Williams, battling to finish the year as world number one at the WTA Championships in Doha, last appeared in the competition in 2007 and was part of the team that won the title in 1999. The 11 times grand slam winner is unbeaten in the competition.
The U.S. are trying to win the Fed Cup for the first time since 2000.
"I am very excited that Serena wants to represent her country," U.S. Fed Cup captain Mary Joe Fernandez said in a statement. "You want to have your best players competing, and Serena is the best in the world."
In the absence of Serena's older sister Venus, 18-year-old Melanie Oudin will get another chance to shine after her run to the U.S. Open quarter-finals.
The team for the tie in Calabria starting on Nov. 7 is completed by doubles specialist Liezel Huber and Alexa Glatch.
(Reporting by Martyn Herman; Editing by Ken Ferris; to query or comment on this story email sportsfeedback@thomsonreuters.com)
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