

In September 2002, Pironkova played in the $10,000 ITF event in Volos, Greece, where she lost only one set playing through the qualifying and main draw. She defeated Tina Schmassmann of Switzerland 7–6(3), 7–5 to win her first professional ITF event.

In January 2006, Pironkova made headlines by defeating tenth-seed Venus Williams in the first round of the 2006 Australian Open by a score of 2–6, 6–0, 9–7. Pironkova was ranked 94th in the world. She lost to Laura Granville in the second round.
In the first round at Wimbledon, Pironkova came from a set down to defeat then top 20 player Anna-Lena Grönefeld 3–6, 6–3, 6–1. In the following round she lost to Agnieszka Radwańska in straight sets.
At the Tier II Proximus Diamond Games in Antwerp in February, Pironkova qualified for the loss of only 10 games in 3 matches, won her first round match for the loss of just two more, and then took a 7–6, 3–1 second-round lead over Belgian World No.1 Justine Henin before losing the match in three sets.
She caused another upset at the 2008 Rome Masters. As a qualifier, she beat top seed and world no. 3 Ana Ivanović in the second round for the biggest victory of her career so far. She advanced to the quarterfinals, her first ever at a Tier I event, when Victoria Azarenka retired during their third round match with Pironkova leading 6–1, 1–0. In the quarterfinals she was defeated 6–2, 3–6, 6–1 by Anna Chakvetadze


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