Chief Executive officers (CEOs) wield significant influence on their companies’ green innovation efforts. Despite considerable prior research on the traits of CEOs and their firms’ green innovation, our comprehension of how the psychological attributes of CEOs impact the course of green innovation remains somewhat constrained. We explore the relationship between three facets of CEO psychological characteristics and their firms’ green innovation. Using upper echelon theory, we posit and show how CEO openness to experience and openness to change affect firms’ green innovation. Besides, we also examine the moderating role of CEO cognitive complexity in these relationships. We formulated measures for CEO psychological attributes through machine-learning algorithms and computer-assisted textual analysis tools, drawing on the language patterns found within the question-and-answer segments of quarterly conference calls with CEOs, and conducted our tests on a sample of 371 CEOs of 277 publicly listed firms. We found that CEO openness to experience CEO openness to change positively influences their firms’ green innovation efforts. Additionally, we found that CEO cognitive complexity enhances the positive influence. Our results maintain consistency after various robustness checks. The findings of our study broaden the scope of research on strategic leadership and its impact on corporate innovation.