Pliskova, who now leads the tour with 48 wins this season, defeated defending champion Caroline Wozniacki of Denmark 6-2, 6-4 in the second match.
Before Sunday Svitolina had won just one set in seven straight harrowing defeats to the Czech but turned the tables to issue a warning to her rivals in White Group.
But the Czech, the only player to have a positive head-to-head record against all three of the player's in her group, overall going 18-6 versus the White Group before the match, struggled to make the difference on serve and off the forehand side.
The Dane used her brilliant backhand to create further openings on the Pliskova serve but a combination of tightness on key points from Wozniacki and solid groundstrokes from the Czech prevented the champion from gaining a foothold.
"I felt pretty good from the baseline today, so it wasn't only down to my serve", Pliskova said in a post-match interview.
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"She started a bit nervous in the beginning, it's always tough to defend a title".
The one-way traffic continued in the second set with Pliskova breaking immediately, saving three break points in the next game to the frustration of her opponent.
"I had to really stay focused and be strong mentality. It was really unfortunate for her, but I'm excited to be back here as a singles player after playing in the doubles competition previous year".
She double-faulted seven times in the match, including on set point in the first for Svitolina.
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The couple were due to meet with Indigenous elders, but they chose to cut back Meghan's schedule for the next couple of days. At last year's Invictus Games in Toronto, Markle was in attendance, but in a separate section from her future husband.
Kvitova, the fourth player to qualify for the final, was left to rue the second chance that she missed on an easy volley: she failed to seal the point, led her opponent to put up a defensive lob and sent the ensuing overhead long.
Kvitova's trademark firepower moved Svitolina around the hard court but the Ukrainian's defence was up to the task.
Svitolina broke in the sixth game and held her nerve to claim just her second victory against Kvitova from nine meetings.
U.S. Open champion Naomi Osaka was drawn in the same group as Angelique Kerber, Sloane Stephens and Kiki Bertens for her debut appearance at the WTA Finals in Singapore.
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