In 1983, at age 39, he became the youngest mayor and Party secretary of a major city, of Shenyang, the capital of Liaoning. In 1987, he became governor of the province, a post he kept until 1990.
As governor, mainland China's first expressway was built in the province, linking the cities of Shenyang and Dalian.
Li served briefly as the Party chief in the agricultural province of Henan in the 1990s. He later moved to serve as Guangdong Party Secretary.