In 2001, Pironkova won the Atlantic Cup International Junior Tournament held in Bulgaria,[4] and her career high in juniors was world no. 227 on March 25, 2002.
In August 2002 at the age of 14, Pironkova played her first professional tournament at the $10,000 International Tennis Federation Tournament in Bucharest, Romania. Pironkova won 3 qualifying matches before reaching the final in the main draw, where she lost to Monica Niculescu of Romania, 6–1, 7–6(1).[6]
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[7] to win her first professional ITF event.[2]
In 2003, she won three ITF singles titles: one in Orestiada, Greece and two in Istanbul.
On the week of May 14–21, 2005, at the age of 17, Pironkova played in her first WTA level tournament, the Tier III event in Istanbul, Turkey. After winning two qualifying matches, Pironkova won three matches in the main draw before she lost in the semi-finals to Venus Williams.[8]
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[9]. Pironkova was ranked 94th in the world.[10][11][12] She lost to Laura Granville in the second round.
Pironkova started the year with early-round losses in Australia - she lost to World no.67 and no.7 seed Anna-Lena Groenefeld in the qualifications in Sydney in three sets (5-7 in the third set) and the second round of Australian Open - after defeating unseeded Galina Voskoboeva with 6-4 6-4, she suffered a 6-1 6-4 loss to World no.28 Shahar Peer.
In February she fell to non-top 100 players Darya Kustova and Tamira Paszek in the qualies in Paris and Dubai (lost to Paszek after 5-7 in the third set; won the first set with 6-1 after leading 5-0).
In early June she suffered second round of qualifying loss to World no.344 and US Open Girl s Champion Heather Watson; it was her 7th non-top 100 loss of the year.Entering Wimbledon with a career 1-4 record at the event, she defeated Anna Lapushchenkova in the first round 6-0, 7-67. In the second round Pironkova beat former Wimbledon Girl's Champion Vera Dushevina 6-3, 6-4 to reach the third round of Wimbledon for the first time in her career. In the third round she defeated rising star Regina Kulikova 6-4 2-0 (ret.). She then defeated the former Wimbledon finalist and number 11 seed Marion Bartoli 6-4, 6-4 in the fourth round. In the quarterfinals, Pironkova shocked second seed and five-time Wimbledon champion Venus Williams 6-2, 6-3 to become the first Bulgarian to reach a semi-final of a Grand Slam tournament after Manuela Maleeva (although Maleeva was playing under the Swiss banner) achieved this feat at the US Open in 1992 and 1993. Pironkova was ranked eighty places lower than Williams, making this defeat for Williams her most lopsided in her time playing at Wimbledon.
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