Although it is well established that the military experience of top executives has a profound influence on firms’ decisions, empirical evidence on how military experience matters to corporate environmental investment has been scarce. Drawn on imprinting theory and upper echelon theory, this study examines the impact of entrepreneurs’ military experience on corporate environmental investment. Using a nationwide survey of Chinese private firms, we find that entrepreneurs’ military experience significantly promotes corporate environmental investment. Further, the positive effect is more pronounced for firms with entrepreneurs who have experienced a wartime atmosphere and those located in regions with more minor public environmental concerns. Our study extends the literature on the determinants of corporate environmental investment and the economic consequences of individual military experience. Moreover, this also provides practical insights for policymakers on how to implement environmental governance and promote ecological construction.