When the incentive mechanism of green finance fails to fully promote green technology innovation in industrial enterprises, local government environmental regulations become an important tool in correcting this market failure. However, due to the “follow the cost” hypothesis, the moderating effect of the local government environmental regulation is heterogeneous. In order to explore the impact mechanism of green finance development on the efficiency of green technology innovation in industrial enterprises, spatial effects as well as the heterogeneous moderating effect of local government environmental regulation, this paper systematically evaluates the development level of green finance in 30 provinces in China from 2009 to 2019. It estimates the efficiency of green technology innovation in industrial enterprises using the super-efficiency SBM model, and empirically analyzes the impact mechanism and moderating effect using the spatial Durbin model. The results show that: (1) green finance not only positively impacts the efficiency improvement of green technology innovation in industrial enterprises but also has significant spatial spillover effects; (2) local government environmental regulation has a nonlinear “inverted U-shaped” moderating effect between the green finance development and the efficiency of green technology innovation in industrial enterprises. Based on the research conclusions, this paper proposes policy recommendations from the perspectives of deepening the regional connectivity of green finance and promoting joint regulation by local governments.