Kuznetsova, seeded fifth, will face Ayumi Morita of Japan. At the Beijing Olympics, Li defeated Kuznetsova 7-6 (5), 6-4.
"I'm happy with the result,'' Kuznetsova said. "I've been working harder and harder since the Olympics. I'm playing better now and am getting back to my normal level.''
Fourth-seeded Dinara Safina of Russia defeated Dominika Cibulkova of Slovakia 6-3, 6-4.
"She's not an easy opponent,'' Safina said. "But I've had almost a week of practice on this surface. It's fast and it suits me. I struggled with my serve and was glad to close it out in two sets.''
Kuznetsova took advantage of unforced errors by Li and closed out the match with an ace.
Kuznetsova helped Russia to a 4-0 win over Spain in the Fed Cup final Monday. She said the travel to Tokyo contributed to her erratic form. She cruised in the first set, but was broken by Li three times in the second set.
"I didn't have much consistency,'' Kuznetsova said. "It's tough coming from overseas. I lost my concentration in the second set, but fortunately was able to come back and win the match.''
Top-seeded Jelena Jankovic received a bye into the second round, along with fellow Serb Ana Ivanovic, who is No. 2 seed.
Jankovic will face Italy's Flavia Pennetta on Thursday while Ivanovic will play Russia's Nadia Petrova.
In other first-round matches, Virginie Razzano of France defeated Japan's Ai Sugiyama 6-3, 6-2; Petrova downed France's Aravane Rezai 7-5, 6-2 and Slovenia's Katarina Srebotnik coasted to a 6-1, 6-2 over Denmark's Caroline Wozniacki.
Usain Bolt Is A Blanco
Russia wins Fed Cup final
