The Williams sisters will play singles and Navratilova and Raymond will team in doubles in a first-round match against Slovenia April 24-25 in Portoroz, Slovenia.
The selections were announced by U.S. Fed Cup captain Zina Garrison.
"I call it a 'Dream Team' for more than one reason," Garrison said. "Martina Navratilova is an incredible person who has done so much for our sport. Venus and Serena are incredible. And Lisa is a good team player who plays singles and doubles well."
Navratilova has a 30-0 Fed Cup record.