In or prior to 616, he was serving as the sheriff of Dong Commandery (東郡, roughly modern Anyang, Henan), when he was accused of crimes and sentenced to death.
The jailer Huang Junhan (黃君漢), who had been impressed with Zhai's bravery, secretly released him at night.
Zhai then fled to nearby Wagang (瓦崗) and gathered a group of men to rise against Emperor Yang of Sui's rule.
Two of his key followers were Shan Xiongxin (單雄信) and Xu Shiji, who suggested him that he could supply his men without pillaging the people of the locale, but that because the Bian River (汴水) flowed through nearby Yingyang (滎陽, roughly modern Zhengzhou, Henan) and Liang (梁郡, roughly modern Shangqiu, Henan) Commanderies and carried heavy river traffic, all they would need to do was to pillage the river traffic.
Initially, the rebel leaders all took him lightly as being overly ambitious, but eventually they began to consider his ambitions justified.
Li therefore suggested to Zhai that, with Emperor Yang away at Jiangdu (江都, in modern Yangzhou, Jiangsu), he should gather his troops and attack Sui's two capitals: Luoyang and Chang'an.
In response, Emperor Yang sent the general Zhang Xutuo (張須陀), who had previously been successful against rebel leaders, to attack Zhai.
The Sui generals Liu Changgong (劉長恭) and Fang Shi (房崱), viewing Zhai's forces as nothing more than bandits looking for food, took them lightly and attacked.
Li made Zhai his prime minister and created him the Duke of Dong Commandery.
Li initially hesitated, believing that this would cause disunity among the ranks, but Zheng finally persuaded him that Zhai was too much of a risk.