This paper uses data from non-financial listed companies in Shanghai and Shenzhen A-share markets from 2011 to 2020 in China to explore the impact of digital finance development on the skilled labor structure of enterprises. The findings suggest that the development of digital finance can significantly optimize the skilled labor structure of enterprises, which is manifested by the increase of the proportion of skilled employees, and this effect is more prominent in high-growth enterprises, high-value-added industries, and regions with a lower degree of marketization. Mechanism testing shows that after effectively alleviating corporate financing constraints, the development of digital finance can not only encourage enterprises to increase the employment demand of highly-skilled labor, but also provide financial space for optimizing the employee incentive system, thereby promoting the upgrading of human capital in enterprises. Further research shows that the development of digital finance significantly improves the labor production efficiency of enterprises while improving their overall operating conditions. This paper not only strongly supports the active exploration of the financial supply-side reform in the new era oriented by “enhancing the capability of financial sectors to serve the real economy”, but also makes a useful expansion of the relevant literature on skilled labor structure and digital finance.