Williams is bidding to win a singles gold medal for the first time and the American fourth seed remains on course to achieve her aim after a third successive demolition job at the All England Club.
The 30-year-old, who faces former world number one Caroline Wozniacki or Slovakia’s Daniela Hantuchova in the last eight, had lost just nine games in her first two matches and she needed only 51 minutes to crush Zvonareva in an almost perfect display under the Wimbledon Centre Court roof.
Williams, a two-time doubles gold medal winner with sister Venus, thrashed Zvonareva in the 2010 Wimbledon final and this match was even more one-sided.
It took just two minutes to determine the course of the match as Serena, a 14-time Grand Slam winner, easily broke the 13th seed in the first game.
Even at this early stage, Zvonareva seemed resigned to her fate and she gave up on one Williams winner without even a token effort to return.
After another break in the fifth game, Williams could have been forgiven for easing up. But she is in business-like mood this week and instead hammered down three successive aces to hold serve before storming back from 40-0 down to seal the set with one more break.
This was ruthless stuff from Williams and the second set was just as painful for Zvonareva, who repeatedly slammed her racquet in frustration as a barrage of Williams winners ended her medal hopes.