The former world number one led France to promotion from the Fed Cup second division during her term.
The former world number one took over as team captain in 2012, leading France to promotion from the Fed Cup second division during her term.
"I am expecting my second child in April and with the Fed Cup programme including matches in February and April, it would be impossible," said the former Wimbledon and Australian Open champion.
Mauresmo, 37, who formerly coached world number one Andy Murray, said she had kept the news secret from the team which fell 3-2 to defeat to the Czechs in Strasbourg on Sunday.
"It was a bit of a shock at first, they weren't expecting it," said Mauresmo after telling the players earlier Monday.
She said that her decision had nothing to do with tension within the team following the defeat.
"This has got nothing to do with the results this weekend nor with any so-called disagreement among the girls. It is simply because it would be impossible to continue."
Mauresmo gave birth to a son in August 2015 when she was Murray's coach. The partnership with the Scot ended in May this year after almost two years with reports at the time suggesting she wanted to spend more time with her son.