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Djokovic dropped his serve to fall behind 2-1 in the opening set but broke back immediately and took control from there against his 32-year-old opponent.
The six-time Grand Slam champion didn't appear to have any problem with his right ankle, which he twisted while representing Serbia in the Davis Cup in April then appeared to hurt again in a second-round loss to Grigor Dimitrov at the Madrid Open last week.
Djokovic has reached the final in four of the five past years at the Foro Italico, winning the title in 2008 and 2011.
In the first round, Julien Benneteau of France eliminated 12th-seeded Nicolas Almagro 7-6 (2), 6-4 and Mikhail Youzhny beat 13th-seeded Tommy Haas 6-4, 6-3 in a match-up of tour veterans.
Also, former top-10 player Fernando Verdasco of Spain defeated Horacio Zeballos of Argentina 6-3, 3-6, 6-3.
In the women's tournament, former No. 1 Caroline Wozniacki lost to 48th-ranked Bojana Jovanovski 2-6, 6-4, 7-6 (5) in the first round.
The 10th-seeded Wozniacki wasted a 5-2 lead in the third-set tiebreaker. The Dane has struggled on clay this season, losing to Yaroslava Shvedova in the first round in Madrid and to Carla Suarez Navarro in her first match in Stuttgart, Germany, last month.
Also, eighth-seeded Petra Kvitova overcame a second-set lapse to beat Sabine Lisicki of Germany 6-4, 0-6, 7-5 and reach the third round.
Also in the first round, 12th-seeded Maria Kirilenko of Russia eliminated Spanish qualifier Anabel Medina Garrigues 6-3, 6-3 and will next face 31st-ranked Varvara Lepchenko of the United States, who defeated Ukrainian qualifier Lesia Tsurenko 6-4, 6-2.
Results on the third day of the ATP/WTA Rome Masters on Tuesday (x denotes seeding):
Men:
Mikhail Youzhny (RUS) bt Tommy Haas (GER x13) 6-4, 6-3
Fernando Verdasco (ESP) bt Horacio Zeballos (ARG) 6-3, 3-6, 6-3
Jeremy Chardy (FRA) bt Feliciano Lopez (ESP) 3-6, 7-5, 7-6 (7/4)
Julien Benneteau (FRA) bt Nicolas Almagro (ESP x12) 7-6 (7/2), 6-4
Gilles Simon (FRA) bt Filippo Volandri (ITA) 6-3, 2-6, 6-4
Viktor Troicki (SRB) bt Lukas Rosol (CZE) 3-6, 6-1, 6-4
Women:
First Round:
Bojana Jovanovski (SRB) bt Caroline Wozniacki (DEN x10) 2-6, 6-4, 7-6 (7/5)
Maria Kirilenko (RUS x12) bt Anabel Medina Garrigues (ESP) 6-3, 6-3
Julia Goerges (GER) bt Andrea Hlavackova (CZE) 2-6, 6-4, 6-4
Varvara Lepchenko (USA) bt Lesya Tsurenko (UKR) 6-4, 6-2
Roberta Vinci (ITA x13) bt Elena Vesnina (RUS) 6-7 (2/7), 7-5, 6-4
Dominika Cibulkova (SVK x14) bt Kristina Mladenovic (FRA) 1-6, 6-2, 6-2
Ursula Radwanska (POL) bt Ana Ivanovic (SRB x15) 6-3, 2-6, 6-2
Christina McHale (USA) bt Karen Knapp (ITA) 7-5, 6-2
Zheng Jie (CHN) bt Madelina Rybarikova (SVK) 7-6 (7/0), 6-3
Yanina Wickmayer (BEL) bt Kirsten Flipkens (BEL) 6-4, 6-0
Second Round:
Petra Kvitova (CZE x8) bt Sabine Lisicki (GER) 6-4, 0-6, 7-5
