A match-up between two of the best exponents of grasscourt tennis always looked like being a classic and it lived up to expectation as 2011 champion Kvitova edged it 5-7 7-6(2) 7-5.
With her last Wimbledon title in 2008 fading into the past, the 34-year-old Williams may be in the twilight of her glittering career but after injury and illness robbed her of some of her powers in recent years, she appears reinvigorated.
Friday’s match would have graced a final, let alone a third round match, such was the level achieved by both players.
“The battle is always a little more enjoyable when you win,” Williams, playing her 63rd grand slam,” told reporters.
“When you lose, there’s so much more to learn from the situation. I think, just for me to be able to play that well having really not played hardly any matches is good. I think I’ll just keep improving.
“People have been trying to retire me since I was like 25. For some reason in tennis we always do that to our players. It’s weird,” she added.
Williams was bidding to reach the last-16 for the first time since 2011 and executed some majestic tennis during a first set in which both players exchanged plenty of heavy metal.
Thundering down first serves reaching nearly 120mph (193kph) and clubbing the ball off the ground, Williams kept her nose in front throughout an absorbing first set in which the sound of racket on ball rumbled around the arena.
Despite being 10 years younger than her lithe opponent, powerful left hander Kvitova was the first to feel the pace and was broken to love in the 12th game.
Kvitova stood her ground as the second set followed a similar pattern to the first with serves dominating but she came alive in the tiebreak to streak ahead and levelled the match when Williams served a double fault.
Williams, who was world number one 12 years ago and in 17 Wimbledons has racked up 73 match wins, the most of any active player, could make no impression on Kvitova’s serve in the decider but still held firm until the bitter end.
Serving at 5-6, however, she slipped 15-40 behind and Kvitova seized her chance to move through.
The Czech was full of praise for her opponent and believes she can still add to her 45 singles titles.
“She’s a huge player, big champion. So we all have respect for her, definitely,” she said.
“I think if she going to be healthy and play some matches and everything like that, she can do it.”
As well as partnering sister Serena in the doubles, with the pair chasing a sixth title here, Venus said she will now be throwing her weight behind her sibling’s attempt to win a sixth singles title at the All England Club.
“I’m fighting with her,” she said. “I’m in the stand rocking back and forth, almost hitting the ball. I’m pretty much right there with her fighting.”
Top seed Serena faces Alize Cornet in the third round.
(Reporting by Martyn Herman, editing by Pritha Sarkar)