"Sharapova has agreed to play the first round," Shamil Tarpishchev, president of the Russian Tennis Federation and their Fed Cup captain, told reporters.
"She is now fully recovered from the problems with her shoulder and again could challenge for the number one spot."
Former world number one Sharapova has struggled to regain her best form after a nine-month lay-off following shoulder surgery at the end of 2008. The Florida-based Russian finished this year ranked 18 in the world.
Sharapova made her first and only other Fed Cup appearance for Russia in a 4-1 victory over Israel in February 2008.
Tarpishchev said 2009 French Open champion Svetlana Kuznetsova, former world number one Dinara Safina, and up-and-coming Anastasia Pavlyuchenkova will complete Russia's line-up for the tie against France in Moscow on February 5-6.
(Reporting by Gennady Fyodorov; editing by Stephen Wood)