Kvitova, the 2011 champion, broke Williams for the first time in the final game to close out the 2 hour, 30-minute match on Centre Court.
The left-handed Czech player had 11 aces and 48 winners. The 30th-seeded Williams had 29 winners.
Williams, winner of seven Grand Slam titles, had lost in the first round in her last appearance at Wimbledon in 2012.
- Sports & Recreation
- Venus Williams
- Petra Kvitova