The 31-year-old is seeking a third Olympic Games gold and second in the Sprint, which concludes on Tuesday's final day of Track Cycling action.
After qualifying in an Olympic record of 10.724, six-time world champion Pendleton met Ekaterina Gnidenko in the first round and advanced with ease, overtaking the Russian on the back straight and easing to a comfortable win.
The Netherlands' Willy Kanis provided the opposition in the second round and again Pendleton's success was comprehensive as she advanced to the best-of-three last eight.
Kanis advanced into the repechage, but there was no such problems for some of Pendleton's chief rivals.
Anna Meares of Australia made it through after beating Monique Sullivan of Canada, while China's Guo Shuang made it through from heat three after out-racing Natasha Hansen of New Zealand.
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