Alexa Glatch of the United States will open against Flavia Pennetta in the Fed Cup final against Italy.
Glatch beat Pennetta 6-1, 6-1 in their only previous meeting in the first round of this year's French Open.
Italy's No. 2 player, Francesca Schiavone, will face U.S. Open quarterfinalist Melanie Oudin in the second singles match Saturday on the clay courts at the Rocco Polimeni club.
Schiavone and the 18-year-old Oudin have also met once before, with Schiavone winning 6-1, 6-1 in Indian Wells, Calif., last year.
Reverse singles are set for Sunday, plus a possible decisive doubles match featuring Italy's Sara Errani and Roberta Vinci against Liezel Huber and Vania King.
The draw for the best-of-five series was released Friday.