Kvitova was due to face Elena Vesnina in the second round at Roland Garros, having already beaten qualifier Greet Minnen in straight sets.
The 11th seed's participation in the second grand slam of the year is over, though, due to a freak injury suffered as she was carrying out media duties after her opening match.
Kvitova - a two-time Wimbledon champion - is hoping to recover in time for the grass-court season following such an unfortunate setback.
"It is with great disappointment that I announce my withdrawal from Roland Garros," she tweeted on Tuesday.
"During my post-match press conference on Sunday I fell and hurt my ankle. Unfortunately, after an MRI and much discussion with my team, I have made the tough decision that it would be unwise to play on it.
"It's incredibly bad luck, but I will stay strong and do my best to recover for the grass court season."