This study uses data of Chinese A-share listed companies from 2012 to 2021 to empirically examine the impact and action mechanisms of executives' green cognition on enterprises' green technology innovation (GTI). The results of Poisson regression show that executives' green cognition have a significant effect on promoting enterprise GTI, with the conclusion remaining valid after endogenous and robustness tests. Moreover, the mechanism test indicates that executive green cognition could promote enterprise GTI by enhancing their ESG performance. Further analyses find that both government environmental regulation and executive overseas experience have strengthened the promotion effect of executive green cognition on enterprise GTI. These findings provide a new action mechanism path for the relationship between executive cognition and corporate innovation and a micro-level theoretical basis for policy recommendations for promoting enterprises’ GTI and ESG practices.