The Czech 20th seed, a finalist in Melbourne in 2019, was crushed 6-2 6-2 by Romanian Sorana Cirstea on John Cain Arena.
Kvitova produced a staggering 39 unforced errors with just seven winners to bow out in 71 minutes.
It continued a mixed record at Melbourne Park for the two-time Wimbledon champion.
Kvitova has now bowed out of a grand slam in the first round 11 times – with four of those coming at the Australian Open.
Cirstea will face either Misaki Doi or Kristina Kucova in this year's second round.
The 31-year-old also beat Kvitova at the Australian Open last year – in the second round.