How to ensure the employment stability and promote the sustainable development of urbanization is an issue worthy of attention. Generally, the existing literature only studies the impact of human capital or industrial structure upgrading on urbanization, but ignores the synergy between them. Based on panel data of 287 cities at or above the prefecture level in China from 1999 to 2016, this paper creatively calculates the matching degree between human capital and industrial structure of different types of cities, and then uses two-step system GMM model to make an empirical analysis of the impacts of human capital-industrial structure matching degree on urbanization. The results show that:1) there is a significant positive linear relationship between human capital-industrial structure matching degree and urbanization, but there will be significant differences due to the size of cities and regional differences. 2) From the perspective of city-sizes' differences, the positive impact of human capital-industrial structure matching degree of small, medium-sized and large cities on urbanization is not as prominent as that of super-large cities. 3) From the perspective of regional differences, compared with the cities in the central and western regions, the human capital-industrial structure matching degree of the small, medium and large cities in eastern cities has a stronger positive impact on urbanization, but for the super-large cities, the situation is just the opposite. The paper urges policy initiatives to pay attention to the sustainability of urbanization, improve the positioning of urban industrial development and employment direction according to cities of different sizes and regions, in order to improve the matching degree between human capital and industrial structure, and promote the process of urbanization.