Under the background of increasingly severe environmental problems, green innovation has become a key way to realize coordinated development of economy and environment. Therefore, it is of great significance to explore the antecedent factors of green innovation. Based on the upper-echelon theory, this study explores the influence of the academic background of top management teams (TMT) on firm's green innovation outcomes and firm performance in Chinese listed companies. This study also discusses three boundary conditions for TMT's academic experience to promote firm's green innovation. The results show that TMT's academic experience promotes green innovation output. Moreover, TMT's academic experience do not have a uniform effect: strict environmental regulation strengthens the relationship between TMT's academic experience and green innovation output, while political connection and innovation input negatively moderate this relationship. Furthermore, green innovation output does not result in better economic benefits for enterprises with top executives who have academic experience, and this condition is observed more in state-owned enterprises. This study reveals the motivation of green innovation and provides a useful reference for enterprises to implement green innovation strategy more effectively.