Rampant corruption exists in China's energy-intensive industries. However, we know little about the nexus of corruption and enterprise green innovation in China's energy-intensive industries. This paper discusses the impact of anti-corruption on enterprises' green innovation and its effect margin. Analyzing the panel data of Chinese listed enterprises in energy-intensive industries from 2009 to 2017, we find that anti-corruption played a positive role in stimulating enterprises' green innovation investments in energy-intensive industries. Then we adopt the instrumental variable approach and difference-indifferences model to alleviate the endogeneity problem. Moreover, we find that research and development investments from state-owned, high-tech enterprises and enterprises in the regions with more government intervention or weaker intellectual property protection were more prominent after the anti-corruption campaign. Finally, political connection played an intermediary role in this process, in which only the government-official political connection worked. Our results highlight the roles of enterprises' attributes and environmental characteristics as important factors in the relationship between anti-corruption and green innovation investments. Policymakers should enhance the control of corruption to boost green innovation in energy-intensive industries.