With the increasingly severe environmental pollution problems, the executives’ green cognition attracts attention. In this paper, Chinese A-share listed companies are selected as research samples to test the impact of executives’ green cognition on corporate environmental performance, and the impact mechanism and heterogeneity of this issue are deeply discussed. The findings are as follows: First of all, the green cognition of corporate executives promotes corporate environmental performance. Secondly, the promotion effect of corporate executives’ green cognition on corporate environmental performance is positively moderated by the corporate governance level. Thirdly, executives’ green cognition can promote corporate environmental performance by improving corporate green technological innovation. Finally, the promotion effect of executives’ green cognition on corporate environmental performance is heterogeneous, and the promotion effect of executives’ green cognition on corporate environmental performance is more significant in the non-state-owned manufacturing enterprises in the central and western regions.