China’s traditional industrial model is characterized by high energy consumption and high pollution, which results in many environmental problems that cannot be ignored. To achieve sustainable development, the Chinese government has proposed five development concepts of “innovation, coordination, green, openness, and sharing”. This initiative highlights the urgency of China’s efforts to strengthen environmental regulation. Based on the panel data of industrial enterprises in China from 2006 to 2015, this study not only investigates the spatial features of technological innovation efficiency, but also examines the relationship between technology innovation efficiency and environmental regulations from a spatial perspective. The results indicate that first, China’s provincial-level technological innovation efficiencies are uneven in space. Second, voluntary regulation positively affects the technological innovation efficiency of industrial enterprises at the provincial level, while mandatory regulation has no significant impact. Third, there is a spatial spillover effect in voluntary regulation at the provincial level. One highlight implication is that the government should promulgate environmental regulations based on each province’s technological innovation potential, due to the spatial differences in technological innovation activities.