No. 7-ranked Sara Errani cruised past Alisa Kleybanova before Flavia Pennetta and Karin Knapp won the doubles.
Errani needed less than an hour to win 6-1, 6-1 against the No. 183-ranked Kleybanova, who has only recently returned to the circuit following treatment for Hodgkin's lymphoma.
Pennetta and Knapp beat newcomers Margarita Gasparyan and Irina Khromacheva 4-6, 6-2, 10-4.
"It's down to a marvelous team and above all the fact that we are always united," Errani said. "We are very happy. It was a very good week for us. I am happy with how I played today."
Italy was favored after Russia traveled without any of its top players, some because of injuries and a scheduling conflict with the season-ending Tournament of Champions in Bulgaria.
However, Roberta Vinci and Errani struggled at times before beating Fed Cup debutants Alexandra Panova and Khromacheva, respectively, on a difficult opening day Saturday to give Italy a commanding lead.
Panova was scheduled to play Errani but Russia captain Shamil Tarpischev opted to replace her with the more experienced Kleybanova.
The 24-year-old, who was ranked 20th before her battle with cancer, was given a warm reception as she walked onto the court.
Errani, who dropped just two games and earned five breaks. A stunning drop-volley handed Errani two match points and although Kleybanova saved one, she netted a volley on the second.
"I knew I had to play yesterday after the two matches," Kleybanova said. "But there was no sort of pressure on me. I tried to do my best, but this is the first official match I've played on clay since 2011. I tried to do my best but Sara was really in form.
"(Corrado) Barazzutti is a captain who really understands his role. He's certainly one of the best. And the girls are really close to each other. They have so much respect."
Italy is now tied with Russia with four Fed Cup titles, one behind Spain. The United States leads with 13, followed by Australia and Czech Republic with seven titles.
Captain Corrado Barazzutti tied Vicky Berner, Billie Jean King and Miguel Margets with four titles as captain.
"Sara was as ever a real champion," he said. "They were all brilliant and I have to thank everyone who contributed to this project and this success."
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