Vinci, No. 13 in the world in singles rankings, goes against world No. 136 Alexandra Panova in Saturday's series opener. Sara Errani, who is seventh in the rankings, takes on No. 183rd-ranked Alisa Kleybanova in the second singles match.
The series is to be played on a red clay court outdoors at Cagliari on Sardinia.
Russia has five players in the WTA's Top 30 but injuries -- notably to fourth-ranked Maria Sharapova -- and other commitments, including No. 18 Maria Kirilenko and 25th-ranked Elena Vesnina playing in the WTA's Tournament of Champions, led
Russian captain Shamil Tarpischev to turn to players outside the rankings' Top 125.
Saturday marks the first Fed Cup match for Panova and Kleybanova hasn't played in the tournament since 2010. Neither Irina Khromacheva nor Margarita Gasparyan, penciled in for doubles Sunday, have played in the Fed Cup.
The Italians, on the other hand, are experienced in Fed Cup play.
Vinci is 22-4 overall, including 4-1 this year. Errani has 27 Fed Cup matches to her credit and is 2-2 this year. They also comprise the world No. 1 doubles team but aren't scheduled to handle that duty this weekend. That falls to Karin Knapp and Flavia Pennetta.
The doubles match comes last in Fed Cup play. Sunday's schedule calls for reverse singles, with Errani meeting Panova and Vinci playing Kleybanova, before Knapp and Pennetta are called on to face Gasparyan and Khromacheva.
Italy is looking for its fourth Fed Cup championship. The Italians first won the tournament in 2006 and added titles in 2009 and '10. Russia also owns four Fed Cup championships, going back-to-back in 2004 and '05 and again in '07 and '08. Russia has been a runner-up five times, most recently in 2011.
Russia holds a 5-1 edge over the Italians in the Fed Cup series. One of the victories came in the 2007 finals.
Beyonce flaunts bikini body, Blue Ivy in vacation pics
Jordana Brewster on Paul Walker: 'He was an enormous presence in my life'