Zvonareva started to compete on the ITF Circuit in 1999, debuting at an ITF tournament in Tbilisi, Georgia. She won three qualifying matches there to reach the main draw before losing in the first round. The next year, she won an ITF event in Moscow, Russia without dropping a set, despite being unranked. The event was just the second event she had played in her professional career. Five weeks later, she made her WTA-level debut at the Tier I tournament in Moscow, beating World No. 148 Elena Bovina before losing to World No. 11 Anna Kournikova in the second round. In 2001, she failed to qualify for WTA events in Key Biscayne, Florida and Moscow, but reached a semifinal at the ITF Circuit tournament in Civitanova, Italy. During this time, she also showed her adeptness in juniors' competition by winning the Orange Bowl under-18s event in 2000 and 2001.Zvonareva won her second ITF Circuit title in Naples, Florida and in July reached her first singles final on the WTA Tour at Palermo, losing to Mariana Díaz-Oliva in three sets. She also achieved semifinal finishes in Warsaw and Sopot plus a quarterfinal finish in Bol. Zvonareva won three qualifying matches at the French Open to reach the main draw for the first time at a Grand Slam tournament. She lost there in the fourth round to eventual champion Serena Williams 4–6, 6–0, 6–1. Her ranking was high enough for a direct entry into Wimbledon where she lost in the second round to 23rd-seeded Iva Majoli 7–6(5), 6–2. At the US Open, Zvonareva lost to World No. 7 Kim Clijsters of Belgium in the third round 1–6, 7–5, 6–4. Her ranking rose into the top 100 after the French Open and into the top 50 after the US Open.
Zvonareva won her first career Grand Slam title, winning the mixed doubles competition at the US Open with Bob Bryan. She won one singles title, in Memphis, Tennessee, and reached the final of the events in Cincinnati, Ohio and Philadelphia, losing to top ten players Lindsay Davenport and Amélie Mauresmo respectively. In the final of the Memphis event, Zvonareva trailed hometown favorite Lisa Raymond 5–2 in the third set before saving three match points and winning the last five games of the match to win the title 4–6, 6–4, 7–5. In addition to this, she reached the semifinals of three Tier I tournaments in Rome, San Diego, and Montreal. She lost in San Diego to fellow Russian Anastasia Myskina, in a match that featured a final set tiebreak that finished 17–15. Zvonareva and Myskina teamed up in the final of the Fed Cup, playing in the crucial final rubber against Marion Bartoli and Émilie Loit, which the pair won 7–6(5), 7–5 to seal Russia's first ever Fed Cup title.Zvonareva ended the year ranked World No. 11, her best year-end ranking back then. In August, she reached her career high of World No. 9. Because of several withdrawals, Zvonareva was able to compete at the WTA Tour Championships, an event reserved for the top eight players in the world. She was unable to win a match and exited at the round robin stage.
Still playing on hard courts, she then reached the final of the Tier I Qatar Total Open in Doha, beating Dinara Safina, Sybille Bammer, and Li Na along the way. In the final against World No. 5 and fourth-seeded Maria Sharapova, Zvonareva lost in three sets. In March, at the Bangalore Open, Zvonareva lost in the quarterfinals to Venus Williams. Zvonareva then reached the quarterfinals of the Tier I Pacific Life Open in Indian Wells, California before losing to eventual champion Ana Ivanović 6–1, 6–4. Two weeks later, Zvonareva reached the semifinals of the Tier I Sony Ericsson Open in Key Biscayne, Florida where she lost to fourth-seeded Jelena Janković 6–1, 6–4.
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