After cruising 6-1 in the first set, Bartoli struggled in the second before breaking Rodionova to secure her first-round win.
Bartoli had planned to skip New Haven, but after playing poorly in Toronto and winning just one match in Cincinnati she decided she needed the work.
"It was important for me to get more matches before the Open started," she said. "I think it's just the perfect preparation. I have some matches here to play. I can practice as much as I want so, it's perfect."
Nineteen-year-old American Christina McHale upset sixth-seeded Svetlana Kuznetsova of Russia 7-5, 6-3.
"I think it's great when we have a lot of Americans in the draw," she said. "But yeah, I'm excited to be in the next round and it's definitely really helpful and it's great to have the crowd behind me."
McHale was down 4-2 in the first set before reeling off three consecutive games, eventually taking the set 7-5. She broke Kuznetsova again to open the second set, one of 11 service breaks in the match, seven by the American.
"If I would have won the serve when I broke her (in the first set) it would have been different," said Kuznetsova, who also lost to McHale in their only other meeting, at Indian Wells in March.
In other matches, 20-year-old Polona Hercog of Slovenia upset Nadia Petrova of Russia 7-5, 7-5, fifth-seeded Agnieszka Radwanska of Poland downed Russia's Ekaterina Makarova 6-1, 6-2 and No. 8 seed Anastasia Pavlyuchenkova needed three sets to advance past fellow Russian Vera Dushevina 3-6, 6-4, 6-3.
Hercog, a 20-year-old clay-court specialist, was broken at 5-4 in the second set, but came back to win the final two games of her match with Petrova, a finalist here a year ago.
She will face three-time defending champion Caroline Wozniacki in the second round on Tuesday.
McHale will play Suarez Navarro of Spain in the second round. Navarro beat Iveta Benesova in straight sets 6-3, 6-2.
In other matches, Maria Kirilenko of Russia defeated Sara Errani of Italy 7-5, 7-5; Roberta Vinci of Italy downed Lucie Hradecka of the Czech Republic 3-6, 6-3, 6-3 and Petra Cetkovska of the Czech Republic beat Ayumi Morita of Japan 6-2, 6-2.
Bartoli downs Rodionova at New Haven
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