Exploring the relationship between industrial green development, technological innovation, and employment structure, especially the impact between industrial green development and technological innovation on employment structure, is of enormous theoretical and practical importance to achieve high-quality employment as well as optimize the employment structure of China. Thirty Chinese provinces’ data from 2009 to 2019 is adopted to assess industrial green development levels. Considering the above, this research innovatively integrates industrial green development, technological innovation, and employment structure into an analytical framework, and empirically investigates the effects of the two factors and their interaction on employment structure by adopting a two-way fixed effects model. The specific conclusions are presented as follows. Firstly, China’s industrial green development levels exhibit a fluctuating and rising time-series evolutionary feature from 2009 to 2019 and have regional differences. Secondly, industrial green development, technological innovation, and their interaction are conducive to optimizing China’s employment structure. Thirdly, the eastern and northeastern areas’ employment structure optimization is boosted by industrial green development. However, the corresponding regression coefficients in the western and central areas are not significant. The northeastern, eastern, and western areas’ technological innovation encourages employment structure improvement. Instead, the employment structure is hampered by technological innovation in the central region. An interaction between industrial green evolution and technological innovation positively affects relevant employment structures in the four regions. Specific results of this research are of necessary theoretical significance and the realistic reference price for whether industrial green development and the interplay affect employment structure.