World number 11 Flavia Pennetta had earlier overpowered Alexa Glatch 6-3, 6-1 to give the hosts a strong start.
Schiavone triumphed having been 4-2 down in the first set when rain forced a two-hour delay. The Italian came back out much the stronger and immediately broke the 18-year-old with an exquisite drop shot. Her opponent then hit the net with an easy shot on serve in the tiebreak, allowing a confident Schiavone to take it 7-2.
Oudin, the top-ranked US player in the team at 49 after Serena and Venus Williams decided not to compete, broke in the first game of the second set but lost the advantage straight way when she missed with a sliced backhand. Schiavone then broke to love to move 3-1 up and although she again carelessly dropped her serve, the win was hers. In the opening match, Pennetta quickly imposed herself and broke Glatch to go 2-1 up thanks to a superb drop shot.
She then sealed the first set when the tall American was broken again after going long.
Pennetta lost focus slightly at the start of the second set, being broken in the first game, but stormed straight back with a graceful winner to level at 1-1 and easily wrapped up the match.
"It was very emotional with the national anthem (before play started). I almost wanted to cry," she told a news conference. Italy are chasing their second Fed Cup title having won in 2006 while US are seeking an 18th crown.
Rain is also forecast on Sunday when the reverse singles and doubles match are scheduled. Pennetta meets Oudin first.
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