Clijsters will line up with compatriot Justine Henin-Hardenne against champions Russia on clay in Liege on April 22-23.
The pair are ranked second and third in the world respectively, but Clijsters said the tie won't be easy.
"We'll have to be at our best as the Russians have two strong top 10 players in Elena Dementieva and Nadia Petrova," said US Open champion Clijsters, who has been playing doubles this week at the Nasdaq-100 Open.
"I'll probably return from the US this weekend and then I can start preparing for the clay season.
"It has been a while though since I played doubles. It's a good exercise as the doubles might be decisive in the Fed Cup meeting against Russia."
Russia, aiming for a third title in as many years, have called up Fed Cup newcomer Maria Kirlienko and Dinara Safina in the absence of the the unavailable Anastasia Myskina, Svetlana Kuznetsova and Maria Sharapova.
