Her decision was announced by the United States Tennis Association.
She made the decision late Saturday before her season-ending match against older sister, Venus, at the Sony Ericsson Championships at Doha, Qatar.
"I think I'm just going to be wiped out by the end of this," Serena said after beat the injured Caroline Wozniacki.
Her decision means Vania King, No. 78 in the latest women's world rankings, gets a chance to better her 4-5 career Fed Cup record.
Team USA Captain Mary Joe Fernandez will use King, Melanie Oudin, Alexa Glatch and Liezel Huber, the world's top doubles player, in the Nov. 7-8 match-up against Roberta Vinci, Francesca Schiavone, Flavia Pennetta and Sara Errani.
Italy has never beaten the U.S. in Fed Cup competition, but Vinci has lost just one of 15 career Fed Cup singles matches.
Copyright 2009 by United Press International.