In recent years, the problem of large-scale production suspension of domestic enterprises and unemployment of laborers brought about by environmental governance is becoming increasingly serious. How to reduce the negative externalities of environmental governance has become an urgent practical problem that needs to be solved. Based on the Cobb-Douglas production function model, this paper introduced the mediating effect model with technological innovation as the intermediate variable to study the impact of environmental governance on employment. We chose Beijing-Tianjin-Hebei and surrounding areas with serious pollution as research objects, and used the panel data from 2005 to 2015 for empirical test. The results show that environmental governance has a positive effect on employment, and the high-intensity environmental governance will stimulate technological innovation, thereby stimulating employment growth. In the process of environmental governance, decision-making departments can not only effectively control environmental pollution by promoting technological innovation, but also reduce unemployment caused by environmental governance.