By revising the new economic geography model, this paper finds that the income gap level among regions determines the spatial spillover effects of human capital agglomeration caused by servitization of industrial structure in surrounding regions. Then, this paper puts forward that the servitization of industrial structure in high-income regions will produce siphon effect and demonstration effect on human capital agglomeration in surrounding areas. Based on the panel data of 30 provinces in China from 2006 to 2019, a spatial vector autoregressive model (SpVAR) was constructed, and the impulse response function was generated with the estimated parameter coefficients using the difference GMM method. The Beijing, Shanghai and Guangdong are selected as three representative examples to plot the impulse responses of human capital in surrounding areas generated by a standard servitization of industrial structure shock occurring. The empirical results verify that the hypotheses are valid in China. Finally, this paper proposes advice from the perspective of coordination relationship between industrial development and human capital agglomeration among regions.