This paper focuses on Chief Executive Officers (CEOs) with green experience, using data from listed companies in China's heavy pollution industry spanning from 2011 to 2021, the study explores the impact of CEO green experience on the Environmental, Social, and Corporate Governance (ESG) performance of companies. The study reveals that CEO green experiences contribute to enhancing firms' ESG performance. The research further unveils that management's green perceptions and corporate green innovations play a partial mediating role in the relationship between CEO green experiences and corporate ESG performance. Heterogeneity analysis indicates that the influence of CEO green experiences on corporate ESG performance is more pronounced in samples characterized by high environmental regulation, capital‐intensive operations, and non‐state ownership. The findings of this study enrich the theory of corporate ESG performance power mechanisms and provide theoretical references for enhancing the ESG performance of heavily polluting firms.