Karolina ranked third in the world, needed just 72 minutes to beat American Williams 6-2 6-2.
Pliskova served five aces as she dominated with her first serve, as the world number eight struggled for rhythm on a slow court.
World number two Muguruza plays French Open champion Jelena Ostapenko later on Sunday.
Venus, the oldest player at this year's tournament at 37, has appeared five times at the end of season event.
The Wimbledon finalist struggled with her serve against Pliskova, hitting six double faults and making 19 unforced errors to Pliskova's 12.
However, Pliskova's persistent showed as she hit 25 winners on her way to a speedy victory.
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