Li, knocked out in the second round by big-serving German Sabine Lisicki 12 months ago, set up a second-round meeting with Romania’s Sorana Cirstea.
Lisicki, the 15th seed, also made the second round with a 6-4, 6-2 win over Croatia’s Petra Martic, who made the fourth round at Roland Garros this year.
Flavia Pennetta, the 16th seed, was knocked out by compatriot and qualifier Camila Giorgi 6-4, 6-3.
In the men’s singles, Novak Djokovic began his Wimbledon title defense in cruise control as he blasted Spain’s Juan Carlos Ferrero off Centre Court to win 6-3, 6-3, 6-1.
The No. 1 seed endured an edgy start and was broken in the third game of the first set, but he struck back immediately and closed out the opener with his usual combination of rugged defense and consistently accurate ground-strokes.
The Serb, who had the honor of opening Centre Court action after beating Rafael Nadal in last year’s final, was in no mood for hanging around and he broke the Spaniard twice in the second set and twice more in the third.
Djokovic next plays either Harrison or Taiwan’s Lu.