Play earlier in the week was washed out in China meaning a hectic schedule on day three, and Kvitova's 6-4 5-7 6-4 exit at the hands of Lin Zhu was the biggest shock.
Since her US Open quarter-final appearance, Kvitova has endured mixed fortunes on tour with her latest exit a second in the first round in three tournaments – the first having come in Wuhan.
Having reached the last four in Beijing the Czech had been expected to ease past her opponent – Zhu ranked 96 places below her.
She quickly realised it would not be so simple, though, as the 23-year-old took the first set thanks to a late flourish.
A topsy-turvy second set went the way of Kvitova, but a capitulation early in the decider in which Zhu raced into a 5-1 lead ultimately proved her undoing.
Kvitova was not the only seed to fall early with 2016 runner-up Alison Riske, Donna Vekic, Lesia Tsurenko and Irina-Camelia Begu also losing – the latter beaten 6-4 6-2 by five-time grand slam champion Maria Sharapova.
After her sensational run to the Wuhan semis, Maria Sakkari continued to impress with a comfortable 6-2 6-1 win over Fangzhou Liu, the Greek sixth seed setting up a meeting with Christina McHale in round two.
All 16 first-round matches were completed on Wednesday as the rain stayed away, with the remaining seeds Shuai Peng and Yulia Putintseva coming through, but 2015 runner-up Danka Kovinic is out after defeat to Xiyu Wang.