In a match-up between the only two Wimbledon champions in the Qatar Total Open draw, Kvitova came out far stronger, reeling off four straight games from 2-all to take the first set in 30 minutes, 6-2.
There's a reason Williams is a seven-time Grand Slam champion and former World No.1 - she has a tendency to lift her game against the elite no matter where she's ranked at the time, as her 119 career wins over Top 10 players demonstrates. She stormed through the second set, 6-2, and built a hefty 4-1 lead in the third set, even holding three points for a seemingly insurmountable 5-1 advantage.
But as quickly as Williams built that third set lead Kvitova evened it up, winning five of the next seven games to push the match to a third set tie-break, and after fighting off a match point down 7-6 in that breaker the No.3-seeded Czech wrapped up the two-hour, 32-minute encounter, 62 26 76(7).
"I obviously put myself in a great position to end the match, which is the positive I take out of this match," Williams said afterwards. "But she played well. I have to give her credit for that. I think I just started to rush a little too much, and maybe I wanted too much of a big shot instead of just working the point and getting the win. Sometimes I think I was just approaching it with the wrong mentality.
"I think I pulled it together towards the end, but she came up with some really great shots."
"She played all out today, and I don't really remember what happened, but I'm happy I was able to come back in the third set," Kvitova said after the match. "I was fighting for every ball and felt really confident on the court, so it was a great feeling for me. In the end, it was just an incredible tie-break.
"Even when she's injured or if she's not playing and then coming back, she's always playing great."
It was somewhat of an opposite result to Kvitova's last match in Doha, a quarterfinal loss to Serena Williams at last year's event - the Czech led 4-1 in the third set of that one before letting it go, and by virtue of that victory Williams regained the No.1 ranking to become the oldest ever World No.1.
"Last year when I came to Doha I didn't really have confidence at the start of the season, and I just came here trying to win some matches," Kvitova said. "When I played Serena in the quarterfinals I played really great tennis. I lost, but I still got some confidence from that for my next matches.
"I remember it quite well. Serena was No.1 after she defeated me, so it was nice for her as well."