From the perspective of enterprise life cycle, the impact of voluntary environmental regulation on enterprise green innovation was examined in this study based on the data of manufacturing enterprises listed on China’s A-share market from 2012 to 2021. The results indicate that: (1) voluntary environmental regulation has a significant positive impact on enterprise green innovation as a whole. (2) Among all stages of enterprise life cycle, voluntary environmental regulation has a significant impact on enterprise green innovation in the growth and maturity stages, but has a relatively small impact on enterprise green innovation in the formation and decline stages. (3) The results of a segmented sample study on this basis show that voluntary environmental regulation has heterogeneity in property rights and factor density in promoting enterprise green innovation. It significantly promotes green innovation by state-owned enterprises in the maturity stage, green innovation by non-state-owned enterprises in the maturity and decline stages, and green innovation by capital and technology intensive manufacturing enterprises, but have no significant impact on other types of enterprises. These research conclusions are expected to provide decision-making reference for improving the voluntary environmental regulation system and promoting the level of enterprise green innovation.