Varvara Lepchenko will play Roberta Vinci in second singles on the indoor red clay court in Rimini, Italy.
Serena and Venus Williams and Sloane Stephens are injured, so Hampton and Lepchenko will make their Fed Cup singles debuts.
The doubles Sunday will feature Melanie Oudin and Liezel Huber against Nastassja Burnett and Karin Knapp.
Italy beat the Americans in back-to-back finals in 2009 and 2010, the first victories against the U.S. after nine straight defeats.
Veterans Francesca Schiavone and Flavia Pennetta, who have struggled lately, were left off Italy’s squad.