Pavlyuchenkova quickly made an emphatic start against Canadian-based qualifier Carol Zhao, winning the first set in 29 minutes on Grandstand Court thanks to a double break of serve.
Zhao responded with aggression in the second set, breaking twice to take full advantage as Pavlyuchenkova was caught taking her foot off the accelerator.
The 18-year-old was unable to maintain that strong start, stuttering on serve as a pair of double faults allowed her Russian opponent to fight back.
In the blink of an eye Zhao's double break was cancelled out, with Pavlyuchenkova rattling off six straight games to claim the match 6-1 6-3.
The world number 31 will now meet former French Open winner Li in the next round, as both players use the hard-court event to build towards the US Open later this month.