Li was born in , Anhui in 1955. He received his LLB, and later a PhD in Economics from Peking University. He entered the top leadership of the Communist Youth League in 1982, and has worked closely with current President Hu Jintao since. He is a representative member of the first generation to have risen from the CYL leadership.
Li became China's youngest governor when appointed to be in charge of Henan, one of China's most populous provinces, in June 1998, at the age of 43. Knowing the complicated situation Henan was in, and the issues associated with networking in the province, Li consciously left his family in Beijing to head to Zhengzhou alone. In addition, according to provincial government officials working with him at the time, Li refused to participate in any banquets or large fancy events not related to government activities.
He is known to be outspoken with a sharp tongue, and led economic development in the central Chinese province, transforming the poor inland region into an attractive area for investment. Li wasted little time in pursuing superficial projects, but rather trekked all regions of Henan trying to search for a comprehensive solution to the province's growing problems. Henan jumped in national GDP rankings from 28th in the early 1990s to 18th in 2004, when Li left Henan.
He was transferred to work as the in Liaoning in December 2004. In Liaoning he is known for the "Five-points to one Line" project, where he linked up Dalian and Dandong, as well as a series of other ports into a comprehensive network. Predictions he would eventually advance to the national level at the 17th Party Congress proved correct when he was elected to the Politburo Standing Committee in October 2007. He was succeeded in his provincial post by Governor Zhang Wenyue.
Li has been touted as a possible successor to Hu Jintao, whose second term as General Secretary, expected to be his last, will end in 2012. At the 2008 National People's Congress, he was elected Vice-Premier, first in rank. This position makes it seem more likely that he will succeed Premier Wen Jiabao.