How enterprises can leverage frontier technologies to achieve synergy between environmental governance and high-quality development has become a critical issue amid the deepening global push for sustainable development and the green economic transition. Based on micro-level data of Chinese enterprises from 2009 to 2023, this study systematically examines the impact of artificial intelligence (AI) on corporate green governance performance and explores the underlying mechanisms. The findings reveal that AI significantly enhances green governance performance at the enterprise level, and this effect remains robust after accounting for potential endogeneity. Mechanism analysis shows that AI empowers green transformation through a dual-path mechanism of “cognition–behavior,” by strengthening environmental tendency and increasing environmental investment. Further heterogeneity analysis indicates that the positive effects are more pronounced in nonheavy polluting industries and state-owned enterprises, suggesting that industry characteristics and ownership structure moderate the green governance impact of AI. This study contributes to the theoretical foundation of research at the intersection of digital technology and green governance, and provides empirical evidence and policy insights to support AI-driven green transformation in practice.