The former Wimbledon and Australian Open champion replaces Nicolas Escude, whose contract has expired.
"Great news. @amemauresmo is the new Fed Cup team captain," the French Tennis Federation said on its Twitter feed.
Mauresmo, who retired in 2009, has been working as a support coach to Belarus's Victoria Azarenka this year.
The 33-year-old has also acted as a grass-court advisor to compatriot Michael Llodra.
The former women's number one was among the world's best players in her 2002-06 heyday, reaching two US Open semi-finals and two quarters at Roland Garros.
She also won the WTA Championships in 2005.