2002 was an inconsistent year for Bondarenko, As she managed to reach the Semifinals in Buchan before losing to Syna Schreiber 2–6 6–4 6–4 and then followed it up by falling in the qualifying draw in Dubai. The following week she was able to reach the second round of Dinan after getting pass the qualifying draw and followed it up by once again failing to qualify now in Tashkent. At her next event in Fontanafredda she was able to qualify for the main draw and win her first ITF title over Italian Mara Santangelo 6–3 6–0. However she again performed badly in her next six tournament managing only to reach one second round, one first-round exit, and failing to qualify in the other four events. She then turned her fortune upside-down once again by reaching her third finals in Batumi but ended up in the losing end. She then made first-round exits in Joué-lès-Tours and Saint Raphael, which were both in France. She ended the year with a semifinals appearance in Poitiers, France, losing to Seda Noorlander 6–2 6–1. In 2003 Bondarenko tried to qualify for the main draw of the WTA tour, but failed to qualify in each, in the 2003 Moorilla International, 2003 Australian Open, and the 2003 Indian Open. She then made it through her first WTA Tour Event main draw as a direct entry at the 2003, but ended up losing to Flavia Pennetta in the very first round 6–3 6–1. She then went back to the ITF tour after failing to qualify in the 2003 Abierto Mexicano Pegaso but was unsuccessful, only making it through one semifinals in Taranto out of seven events. She also failed to qualify for the 2003 French Open and 2003 Wimbledon. In the middle of the two Slams she was able to make it the quarterfinals of the ITF circuit in Galatina and Fontanafredda. She then once again tried to get through the main draw of the WTA tour but failed each time including the 2003 US Open. However following the US Open she was able to win her second ITF title in Zhukovskiy. The bad fortune continued for Bondarenko as she exited in first round of ITF events in Dubai and Prague and the first round of her second amin draw appearance in the 2003 Volvo Women's Open.
The start of 2004 was similar to the previous year, Bondarenko failed to qualify to the main draws of the WTA tour in the 2004 Moorilla Hobart International, 2004 Australian Open, and 2004 Cellular South Cup. However in the 2004 Copa Colsanitas, she qualified for the first time in the main draw and even claim her first victory in the main draw, when she defeated Nuria Llagostera Vives 6–7(1) 6–1 6–1 before being double bangled by eventual champion Fabiola Zuluaga in the next round. After failing to qualify in the 2004 Abierto Mexicano Telcel, she then went back to the ITF circuit were she won her third ITF title in Bari, Italy prevailing over younger sister Kateryna Bondarenko in the finals 2–6 6–2 6–4. In her next tournaments following the title victory, Bondarenko had a bad run failing to qualify in any of the WTA Tour events she entered while falling early in the ITF events she entered. She then reached the finals of Orbetello, Italy, losing to Catalina Castaño 2–6 6–2 6–3. She then made little progress as she only managed to make two quarterfinal appearance in the ITF circuit and once again failing still to qualify in the WTA events. She ended the year with a runner-up performance in Deauville, France, losing to Květa Peschke 6–0 6–3 and quarterfinal appearances in the ITf events in Poitiers and Bergamo 2. 2005, was sort of a better start of the year for Bondarenko, even though failing to qualify in the 2005 Moorilla Hobart International. she made her grand slam debut at the Australian Open, where she suffered a first round loss to sixth-seeded Elena Dementieva of Russia, 6–3 6–3. Two weeks later, she reached her first WTA tour quarter-final at 2005 Volvo Women's Open, Thailand, where she lost to eventual runner-up, Anna-Lena Grönefeld of Germany, in straight sets 6–4 6–1.
The following week at 2005 Hyderabad Open, she reached her first tour final as the tournament's ninth seeded player, falling to hometown favourite Sania Mirza, in three tight sets 6–4 5–7 6–3 . Following her loss, she made her first appearance in the women's top 100 rankings. She then followed it up by qualify for her first Tier 1 event in the 2005 Pacific Life Open, and made through the second round before falling to top American doubles player Lisa Raymond 4–6 6–3 6–3. She also qualified in the 2005 NASDAQ-100 Open but lost in the opening round to Russian Alina Jidkova 6–3 6–2. She however failed to qualify in her next two events in the 2005 Bausch & Lomb Championships were she lost to sister Kateryna Bondarenko and the 2005 Family Circle Cup. She then received a direct entry in the 2005 Estoril Open reaching the second round before losing to 3rd seed Gisela Dulko 6–2 6–3. In the 2005 Telecom Italia Masters Rome she fell in the qualifying round. She then received direct entry in the 2005 Istanbul Cup, 2005 French Open, 2005 DFS Classic, all losing in the first round and failed to qualify in the 2005 Hastings Direct International Championships. She however made a shocking performance in the 2005 Wimbledon Championships, claiming her first Slam win and upsetting 20th seed Tatiana Golovin in the first round 6–3 3–6 7–5, before falling to Natalie Dechy 6–1 6–4 in the third round. She then made early exits in 2005 Internazionali di Modena, 2005 Internazionali Femminili di Palermo, 2005 Nordea Nordic Light Open and the 2005 US Open. Her last good performance of the year was in the 2005 Wismilak International were she reached the quarterfinals before losing to Li Na after defeating top Australian Player Alicia Molik in the previous round. The end of the year was a bad streak for Bondarenko making early exits and failing to qualify in some events. She ended the year for the first time inside the top 100 at 73. 2006 was a breakthrough year for Bondarenko as she made it inside the top 50. The beginning of the year was mixed for Bondarenko, with a quarterfinal appearances in the 2006 Moorilla Hobart International and the 2006 Bangalore Open, and first-round exits in the 2006 Pattaya Women's Open and the 2006 Australian Open. She then made early exits in Dubai, Doha, and Indian Wells. With her early exit in Indian Wells, Bondarenko decided to compete in Orange in California, USA an ITF event claiming the title over Yvonne Meusburger 6–3 7–5. Following the title win she maid stellar performances in the WTA tour, making it to the third round of the 2006 Pacific Life Open entering as a qualifier, losing to Ana Ivanović 6–3 5–7 6–3.
On the Clay season she made it through the second rounds of top events at the 2006 Bausch & Lomb Championships, losing to Vera Dushevina 6–1 6–4, and the 2006 Family Circle Cup, losing to eventual champion Nadia Petrova 6–1 0–6 6–2, the second set was the least games Petrova won in a set in the whole tournament. She made it through the quarterfinals of 2006 ECM Prague Open, losing to eventual champion Shahar Pe'er 7–5 6–0 and the semifinals of 2006 GP SAR La Princess Lalla Meryem, losing to Martina Suchá 6–3 6–2. Her luck, however, was turned upside-down when she made first-round exits in the 2006 Istanbul Cup, 2006 French Open and 2006 DFS Classic. She then made it through the second round of the 2006 Ordina Open before falling to Jelena Janković 6–4 1–6 7–6 and made a first-round exit in Wimbledon. In her 2006 US Open Series tournaments she lost in the first rounds of 2006 Bank of the West Classic and 2006 Rogers Cup, the second rounds of 2006 Acura Classic and the 2006 US Open, and the Third Round of the 2006 JPMorgan Chase Open. In her first tournament after the US Open, she won her first title in the 2006 Fortis Championships Luxembourg ousting Francesca Schiavone 6–3, 6–2 in the finals, the win meant that she was the second lowest-ranked player ever to win a Tier II title, being ranked a lowly number 62. The record is held by Kim Jones-Schaefer who was ranked number 64. She also made it through the top 50 after her first title. She then failed to qualify in the 2006 Kremlin Cup and the 2006 Zurich Open. She ended the year win a first-round exit in 2006 Generali Ladies Linz after getting pass the qualifying round. She ended the year ranked number 32. Bondarenko started the year with a second-round loss to Alicia Molik at the 2007 Moorilla Hobart International 6–3 7–5. At the 2007 Australian Open she made a valiant effort, beating two unseeded players to advance to the third round, losing to 4th seed Kim Clijsters. She then lost in the first round of the 2007 Qatar Total Open, third round of 2007 Indian Wells Masters and second round of the 2007 Miami Masters. She was also able to reach the third round of the 2007 Bausch & Lomb Championships, losing to Jelena Janković.
On 7 May 2007 she finished runner-up to Justine Henin at the Tier II J&S Cup held in Warsaw, Poland, losing 6–1, 6–3. In the semi-finals, she got the first top ten win of her career over then number five Svetlana Kuznetsova in straight sets 6–2, 7–6. The performance saw her rise into the top 30 for the first time, at Number 29. she then followed it up with third-round appearances at 2007 Qatar Telecom German Open and 2007 Internazionali BNL d'Italia, losing to Serbians Ana Ivanović and Jelena Janković respectively, which both of them eventually captured the title. She followed it by making the semi-finals of the 2007 Istanbul Cup, losing to Elena Dementieva 7–6 6–2, once again the eventual champion, this the fourth time in a row that she has lost to the eventual champion. Despite this good performances she lost to an unseeded and lower-ranked Karin Knapp of Italy in three sets. She however bounced back with good showings at the grass season, reaching the quarterfinals of both the 2007 DFS Classic and 2007 Ordina Open, losing both to Jelena Janković; this was her fourth loss to Janković in the year. She then hit her career high shortly after Wimbledon, where she made the third round before losing to Patty Schnyder 6–4, 3–6, 8–6 after holding a 4–1 lead in the final set. She then came out with a 3 straight loss in the second round of the 2007 Acura Classic, first rounds of 2007 East West Bank Classic and 2007 Rogers Cup. but she rebounded just before the Us Open with a quarterfinal showing at the 2007 Pilot Pen Tennis, she then eventually reached the third round of the 2007 US Open, losing to Venus Williams. She then lost 3 straight matches in a row, two of them coming from Frenchwoman Marion Bartoli. On 17 October 2007 Bondarenko beat Amélie Mauresmo 2–6, 6–4, 6–1 at the 2007 Zürich Open to reach her first ever Tier I quarter-final, but lost to Nicole Vaidišová there. She also reached the quarterfinals of the 2007 Generali Ladies Linz, losing to eventual champion Daniela Hantuchová. She ended the year at no. 22. On 22 October she passed $1 million in career prize money, the first player representing Ukraine to pass that prize money milestone.
The Beginning of the year for the Ukrainian wasn't fruitful to say the least, With second-round exits at the 2008 Moorilla Hobart International and 2008 Australian Open, losing to lower-ranked players. Alona, on the other hand, won the Australian Open women's doubles title, partnering with her younger sister Kateryna. They defeated the pairing Shahar Pe'er and Victoria Azarenka 2–6, 6–2, 6–4. They became only the second pairing of sisters to win the title, the first being the Williams sisters. She then followed it up with first-round exits at 2008 Open Gaz de France and 2008 Proximus Diamond Games, once again losing to lower-ranked players. She also lost to eventual champion Elena Dementieva at the 2008 Dubai Tennis Championships in the second round. She made her first third round of the year at the 2009 Pacific Life Open, losing to Maria Sharapova, this was the start of good showings from the Ukrainian. She however lost to Kaia Kanepi in the second round of the 2008 Sony Ericsson Open, after receiving a bye. Continuing her good form from Indian Wells she reached the quarterfinals of 2008 Bausch & Lomb Championships, 2008 Qatar Telecom German Open, and 2008 Internationaux de Strasbourg. In the middle of this she lost in the second round of 2008 Internazionali BNL d'Italia reasonably to Serena Williams. Her performance at a Major once again was a disappointment as she lost in the first round of the 2009 French Open to Petra Cetkovská. She then again made great showing at the grass when she reached the quarterfinals of 2008 DFS Classic and the semi-finals of the 2008 Ordina Open, losing to eventual champion Tamarine Tanasugarn, she however lost at the second round of the 2008 Wimbledon. She then represented Ukraine at the 2008 Olympics, losing to Serbian Jelena Janković in the second round, in the doubles she partnered with sister Kateryna were they came in fourth place. She then reached the third round of the 2008 US Open, losing to Venus Williams. She then lost in the second rounds of 2008 Porsche Tennis Grand Prix and 2008 Zürich Open nad the first round of 2008 Kremlin Cup, this seems like a disappointment for Alona, however she lost to higher rankes players Jelena Janković, Venus Williams, and Katarina Srebotnik respectively. She ended the year competing in the 2008 Generali Ladies Linz were she lost in the quarterfinals to Marion Bartoli.
At the 2009 French Open, Bondarenko fell to 20th seed Dominika Cibulková in the first round in three sets. She then performed badly at grass unable to duplicate her performance in the past two years, losing in the second round of the 2009 Ordina Open and first round of 2009 Wimbledon to Elena Baltacha. She then made it to her first Semifinal since the 2007 Istanbul Cup, shich was more than 2 years ago. She then lost to sister Kateryna 6–1 6-3in the first round of 2009 ECM Prague Open breaking the tie between the two as she trails her sister 3–4 in head-to-head now. She then reached the third rounds of 2009 LA Women's Tennis Championships, losing to Sharapova in three and 2009 Rogers Cup, losing to Serena. She then reached the second rounds of 2009 Western & Southern Financial Group Women's Open nad 2009 Pilot Pen Tennis. In the first round of the 2009 US Open she beat Alla Kudryavtseva 3–6, 6–3, 6–2. However, she lost to Gisela Dulko in the second round. In her first tournament since the US OPen, she lost in the first round of the 2009 Toray Pan Pacific Open to Vera Dushevina 1–6 7–5 6–1. She lost in the third round of the 2009 China Open to Svetlana Kuznetsova 6–3 4–6 6–0 after defeating Ágnes Szávay and Sara Errani both in straight sets. She played her last tournament of the year at the 2009 Kremlin Cup, were she beat Anna Chakvetadze, Nadia Petrova and Tsvetana Pironkova all in straight sets before losing to eventual champion Francesca Schiavone in the semifinals in straight sets as well. Bondarenko started the year with her pre-Australian Open tournament at the 2010 Moorilla Hobart International were she dominated 2nd seed Shahar Pe'er 6–2 6–4 in the finals after defeating Sybille Bammer 6–4 6–1, Alizé Cornet 6–4 3–6 6–2, Zheng Jie 7–5 7–5 and top seed Anabel Medina Garrigues 4–6 6–3 6–4. This title is her 2nd overall and her 1st title in over 3 years. Bondarenko has advanced, as the #31 seed, to the 4th round of the 2010 Australian Open, which is the farthest she has advanced in a Grand Slam tournament. She scored a big straight sets win in the 3rd round over #8 Jelena Janković, but then fell to Jie Zheng in the fourth round, 6–7, 4–6. She then suffered a 4 match losing streak in the first round of 2010 Dubai Tennis Championships, second rounds of 2010 BNP Paribas Open and 2010 Sony Ericsson Open and the first round of 2010 MPS Group Championships. She ended the losing streak in 2010 Family Circle Cup with a straight set 6–4, 6–2 victory over Julie Ditty. She then defeated Bethanie Mattek-Sands 4–6, 7–5, 7–5 before losing to eventual finalist Vera Zvonareva 6–2, 6–1.