In a match in which both players smashed the ball across the net for a succession of blistering winners, the Russian 21st seed played with far greater control on the big points and made fewer mistakes than her American opponent.
The key match statistic was that Pavlyuchenkova made just seven unforced errors, compared with 27th seed Vandeweghe's 22.
So great was the American's frustration at her erratic play that, after she was broken for the second time in the second set, she gave her racket away to a delighted child in the crowd.
Pavlyuchenkova, who turned 25 on Sunday, was one of four Russians to reach the fourth round at Wimbledon - the most since 2009.