Taking the listed companies of China’s heavy pollution manufacturing industry from 2011 to 2019 as the research object, this paper studies the influencing factors and mechanism of CEO power and green innovation on the sustainable development performance of enterprises. The results show that: the greater the CEO’s power, the more it can promote the improvement of enterprise sustainable development performance; green innovation plays a mediating role in the influence of CEO’s power on enterprise sustainable development performance; economic policy uncertainty negatively moderates the mediating role of green process innovation between CEO’s power and corporate environmental & social responsibility performance, and the mediating role of green product innovation between CEO’s power and corporate financial performance. Accordingly, enterprises should reasonably allocate and appropriately increase the power of the CEO, pay attention to the impact of green innovation on the sustainable development performance of enterprises, and have an in-depth understanding of external risks and adverse impacts brought about by changes in economic policies, and take effective countermeasures in a timely manner to effectively improve the sustainable development performance of enterprises.