We explore how CEOs’ pro-nature values—imprinted through early-life experiences—affect green technology innovation (GTI) in heavily polluting industries. These environmental preferences serve as behavioral priors influencing strategic choices, even in the face of economic trade-offs. Using Chinese firm-level data from 2013–2023, we find that CEOs with a strong nature orientation promote greater green technology innovation (GTI). This relationship is amplified by higher CEO educational level and stronger corporate governance but attenuated by firms’ degree of internationalization and financial constraints. Our findings support the view that executive personality traits and environmental beliefs shape firm-level innovation through behavioral pathways.