The 17-time Grand Slam champion powered through the first set against the world number 42 for the loss of just one point on her own serve.
Peng showed more resistence in the second, but couldn't convert on two break points and Williams needed just one chance to seal the only break of the set before serving out the match to set up a third round meeting with Spain's Carla Suarez Navarro or fellow American Alison Riske.
Fourth seed Simona Halep also had a comfortable passage into round three as she saw off Spain's Lara Arruabarrena 6-4, 6-4.
"This tournament means a lot for me, because the last year it was a real turning point for me. I'm really happy that I could win today in two sets to be in third round here," said the Romanian who could face compatriot Irina-Camelia Begu next should she overcome 15th seed Sabine Lisicki.
In the men's Masters tournament, sixth seed Thomas Berdych stretched his perfect record against South African Kevin Anderson to 11-0 with a 6-1, 6-4 win.
"I always like to play here. The courts are great, very well prepared. It's a bit faster because of the altitude, which suits my game well and means I can serve well and play aggressively," said the Czech.
"I think we have similar games, but I can always find something extra and that's the difference. It's also probably a mental thing as well now."
Polish lucky loser Lukasz Kubot made the most of Roger Federer's withdrawal to be at the birth of his twin sons on Tuesday by beating Frenchman Gilles Simon 7-5, 2-6, 6-4.
Latvia's Ernests Gulbis also moved into round three with a 6-3, 6-4 win over Ukrainian Alexandr Golgopolov.
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