This paper, based on the panel data of 13 cities in Hunan Province from 2003 to 2012, establishes a coupling model of human capital and industrial structure system, and analyzes empirically the coordinated development between the two. Results show that, first, the composite index of human capital is higher than that of industrial structure in the 13 cities. Second, the matching degree of the two is generally good, with a big gap between the cities though. Third, the human capital of universities and colleges in Changsha, Zhuzhou and Xiangtan has not exploited its advantages to the full. Therefore, it’ s necessary to promote industrial structure reform when increasing investment in human capital, to establish a docking mechanism of major setup in universities and industrial structure, and an innovative system of industrial structure based on the accumulation of human capital.