2002 was an inconsistent year, as she managed to reach the semifinals in Buchan before losing to Syna Schmidle in three sets and then followed it up by falling in the qualifying draw in Dubai.

At her next event in Fontanafredda, she qualified for the main draw again, and won her first ITF title (final against Mara Santangelo).

She then made it through her first WTA Tour main draw as a direct entry at the Copa Colsanitas, but ended up losing to Flavia Pennetta, 3–6, 1–6.

She then went back to the ITF Circuit, after failing to qualify in the Abierto Mexicano, only making it through one semifinal (in Taranto) out of seven events.

At the beginning of 2004, Bondarenko qualified for the first time and even claimed her first victory there, when she defeated Nuria Llagostera Vives in three sets before being double-bageled by eventual champion Fabiola Zuluaga in the next round.

After that she then went back to the ITF Circuit where she won her third title in Bari, prevailing over younger sister Kateryna in the final, 2–6, 6–2, 6–4.

She ended the year with a runner-up performance in Deauville, losing to Květa Peschke 0–6, 3–6, and quarterfinal appearances in the ITF events of Poitiers and Bergamo.

In 2005, Alona made her Grand Slam debut at the Australian Open, where she suffered a first-round loss to sixth-seeded Elena Dementieva, 3–6, 3–6.

Two weeks later, she reached her first WTA Tour quarterfinal at the Thailand Open where she lost to eventual runner-up, Anna-Lena Grönefeld, in straight sets.

The following week at Hyderabad, she reached her first tour final as the tournament's ninth seeded player, falling to hometown favourite Sania Mirza in three tight sets, 4–6, 7–5, 3–6.

She then qualified for her first Tier-I event in the Indian Wells Open, and reached the second round before falling to top doubles player Lisa Raymond 6–4, 3–6, 3–6.

She received a direct entry to the Estoril Open, reaching the second round before losing to third seed Gisela Dulko.

She then received direct entry in the İstanbul Cup, French Open, Birmingham Classic, all losing in the first round and failed to qualify in the Eastbourne International.

Her last good performance of the year was in the Wismilak International where she reached the quarterfinals before losing to Li Na after defeating top Australian player Alicia Molik in the previous round.

With her early exit in Indian Wells, Bondarenko decided to compete in Orange, California, an ITF event, claiming the title over Yvonne Meusburger 6–3, 7–5.

Then she made stellar performances in the WTA Tour, making it to the third round of the Indian Wells Open entering as a qualifier, losing to Ana Ivanovic 3–6, 7–5, 3–6.

On the clay-court season, she made it through the second rounds of top events at the Amelia Island Championships, losing to Vera Dushevina 1–6, 4–6, and the Family Circle Cup, losing to eventual champion Nadia Petrova 1–6, 6–0, 2–6, the second set was the fewest games Petrova won in a set in the whole tournament.

At the Australian Open she made a valiant effort, beating two unseeded players to advance to the third round, losing to fourth seed Kim Clijsters.

She followed it by making the semifinals of the İstanbul Cup, losing to Dementieva 6–7, 2–6, once again, and this was the fourth time in a row that she has lost to the eventual champion.

She however bounced back with good showings at the grass season, reaching the quarterfinals of both the Birmingham Classic and Rosmalen Open, losing both to Janković; this was her fourth loss to her in that year.

She then hit her career high shortly after Wimbledon, where she made the third round before losing to Patty Schnyder 4–6, 6–3, 6–8 after holding a 4–1 lead in the final set.

On 17 October 2007 Bondarenko beat Amélie Mauresmo 2–6, 6–4, 6–1 at the Zurich Open to reach her first ever Tier-I quarterfinal, but lost to Nicole Vaidišová there.

On the other hand, Bondarenko won the Australian Open women's doubles title, partnering with her younger sister Kateryna.

She made her first third round of the year at the Indian Wells Open, losing to Maria Sharapova, this was the start of good showings from the Ukrainian.

She reached the quarterfinals of Birmingham by defeating Virginia Ruano Pascual and Sunitha Rao before falling to Marina Erakovic.

Alona also reached the semifinals in Rosmalen, losing to eventual champion Tamarine Tanasugarn, she however lost at the second round of 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 and they came in fourth place.

She lost in the third round of the China Open to Svetlana Kuznetsova 3–6, 6–4, 0–6 after defeating Ágnes Szávay and Sara Errani both in straight sets.

[16] Seeded 29th at the US Open, Alona reached the third round after victories over Vera Dushevina and last year quarterfinalist Melanie Oudin.

[19] Alona played her final tournament of the season at the Kremlin Cup, and was defeated in the second round by eighth seed María José Martínez Sánchez.