How to maximize the role of human capital in promoting the upgrading of manufacturing exports, and under what conditions its promotion can maximize its effects, is an important issue in the high-quality development of the new era. Based on the structural and dynamic evolution characteristics of human capital, this paper examines the impact of the evolution of human capital structure on the export upgrade of manufacturing. Firstly, a theoretical model is established to demonstrate that the dynamic evolution of human capital structure from low to high can achieve the role of promoting the technical content of export products. Then, use the 2005-2015 provincial panel data to empirical research. The empirical results show that: Firstly, the dynamic evolution of human capital structure from low to high significantly promotes the export upgrade of manufacturing. This conclusion is still robust considering the measurement error, periodic shock, missing variable bias and endogeneity. Secondly, compared with the human capital stock, the human capital structure with structural problems and dynamic evolution characteristics is more advanced. Conducive to promoting the export upgrade of manufacturing industry, the estimated coefficient is more than twice the estimated coefficient of human capital stock. This conclusion is more prominent under the instrumental variable. Thirdly, the spatial heterogeneity test results show that the promotion of export upgrading is significant in the eastern region, not significant in the central and western regions, and the estimation of instrumental variables remains the same. Finally, from the perspective of economic development effects and market competition effects, this paper researches the nonlinear threshold effect of the upgrading of human capital structure on the export of manufacturing industries. Only when the economic development reaches a certain level and the market competition reaches a certain level, the advanced human capital structure will play a significant role in promoting the export upgrade of the manufacturing industry. Based on these conclusions, this paper believes that human capital which considers structural and dynamic evolution characteristics can better promote the export upgrade of manufacturing industries. And at the same time, the promotion of human capital will be the biggest when economic development and market competition reach a certain point.