The environmental law enforcement supervision from the central government is an important part of China’s environmental governance. Based on the quasi-natural events of environmental protection talks, this paper examines the impact of environmental law enforcement supervision on the corporate green transformation and its mechanism based on the theory of legality and deterrence theory. The study finds that environmental law enforcement supervision significantly promotes the corporate green transformation; the promotion mainly occurs in the next year of the arranged supervision talks of environmental protection; the positive impact of environmental law enforcement supervision on corporate green transformation mainly exists in state-owned enterprises, large-scale enterprises, low-financing and restricted enterprises, and heavy-polluting enterprises. The channel exploration finds that environmental law enforcement supervision promotes the corporate green transformation by reducing the efficiency of enterprise operations, increasing the environmental costs of enterprises, and improving environmental penalties. The conclusions of the study reveal the long-term economic consequences of environmental law enforcement supervision, and provide important enlightenment for improving China’s environmental supervision system and promoting the high-quality economic development.