Human capital plays an increasingly important role in economic growth. Urbanization, urban concentration and other factors influence the accumulation of human capital based on the intensity of economic agglomeration. Urbanization stimulates supply and demand of human capital, and creates favorable investment environment to promote human capital accumulation. Because of the co-existence of scale advantage and external diseconomy, the increase of urban concentration has double effects on human capital accumulation. Considering the heterogeneity and spatial dependence of provinces, empirical analysis is carried out by the nonlinear panel data model and spatial Durbin model according to panel data of 30 provinces from 2000 to 2015. The results show that urbanization has a significant promoting effect on human capital accumulation. There is an inverted U relationship between urban concentration and human capital. It shows obvious differences about the effect of urban concentration on human capital in four regions. The impact of urbanization and urban concentration on human capital is robust. The conclusions have enlightenments for promoting highquality development of urban and regional economy.