The two nations are meeting in the Fed Cup for the fourth time in six years, with the Italians winning the last two matchups.
Pennetta rallied Saturday from a service break down in both of the last two sets to defeat former World No. 1 Amelie Mauresmo 2-6, 7-6 (9-7), 6-4.
Schiavone followed with a 6-1, 2-6, 8-6 win over Alize Cornet.
Sunday's doubles matchup pits the French duo of Severine Bremond and Nathalie Dechy against Italy's Sara Errani and Roberta Vinci.
If a singles match is needed to settle a winner, the schedule calls for Cornet-Pennetta and Mauresmo battles Schiavone if necessary.