The fifth-ranked Kuznetsova, who is a two-time runner-up at the Foro Italico, has not put together three consecutive wins since reaching the fourth round of the Australian Open in January. The 37th-ranked Kirilenko improved to 3-0 in her career over Kuznetsova.
Kuznetsova claimed the second Grand Slam title of her career when she won last year's French Open and the Rome tournament is an important clay-court warmup for Roland Garros, which begins in three weeks.
Kirilenko broke serve to end the match when Kuznetsova landed a backhand into the net.
Earlier in first-round action, Bethanie Mattek-Sands beat United States Fed Cup teammate Melanie Oudin 6-1, 6-3; No.
13 Francesca Schiavone of Italy rallied to eliminate Daniela Hantuchova 3-6, 6-2, 6-2; and No. 16 Shahar Peer of Israel easily defeated Italian wild card Corinna Dentoni, 6-2, 6-1.
Nine of the top-10 ranked players are in action at the tournament - No. 8 Samantha Stosur withdrew following her defeat by Justine Henin in the final of the Porsche Grand Prix on Sunday.
The top eight seeds have first-round byes.
Henin and fellow Belgian player Kim Clijsters did not enter.
Mattek-Sands won key singles and doubles matches back-to-back to lead the Americans to a 3-2 win over Russia in the Fed Cup semifinals eight days ago and she maintained that form against Oudin.
The 31st-ranked Oudin struggled with her serve, holding only three times and winning just 46 percent of the points with her first serve to Mattek-Sands' 81 percent.
The 128th-ranked Mattek-Sands improved to 3-0 in her career against 18-year-old Oudin, who reached the US Open quarterfinals in September.
