Pavlyuchenkova had the early advantage with a break that put her up 3-1 in the first set before Williams came back with two breaks and a hold to win the set.
Williams goes against Israeli Shahar Peer, who advanced when eighth-seeded Na Li retired with a back injury in the semifinals. Peer was ahead 7-5, 3-0 when the match was stopped. Williams won in straight sets both previous times she played Peer.
The other semifinal Friday sends No. 4-seeded Victoria Azarenka against seventh-seeded Agnieszka Radwanska, who have split their four career meetings.
Azarenka advanced out of the quarterfinals with a 6-1, 6-3 win over Vera Zvonareva, who won last week's WTA tournament in Thailand. Azarenka piled up six service breaks in the match.
Radwanska defeated Regina Kulikova 3-6, 6-4, 6-3 in her Thursday match.
Friday's winners will square off Saturday with the tournament title and $350,000 at stake.
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