Frances Tiafoe will be Williams' partner for the United States, while Belinda Bencic will again represent Switzerland with Federer to defend the title they won in January over Kerber and Zverev in the final.
Williams and Federer are scheduled to play mixed doubles against each other when the U.S. meets Switzerland on Jan. 1.
The eight-country tournament is scheduled from Dec. 29 to Jan. 5 on indoor hard courts at Perth Arena. It used by the players as a tune-up event for the Australian Open which begins Jan. 14 in Melbourne.
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Teams announced Wednesday:
Australia: Matt Ebden and Ashleigh Barty
France: Lucas Pouille and Alize Cornet
Germany: Alexander Zverev and Angelique Kerber
Britain: Cameron Norrie and Katie Boulter
Greece: Stefanos Tsitsipas and Maria Sakkari
Spain: David Ferrer and Garbine Muguruza
Switzerland: Roger Federer and Belinda Bencic
United States: Frances Tiafoe and Serena Williams