This study aims to examine how female CEOs influence green innovation and whether firm size moderates this connection. Our paper focuses on CEOs, who are considered the strategic leaders of corporations, because of their crucial role in making important decisions. This research paper examines how female CEOs influence green innovation (GI) in the Asian industrial sector. The primary goal is to address these research questions: Do Asian industrial firms with female and male CEOs differ in their GI efforts? Is there a positive moderating influence of Asian industrial enterprises’ size on the nexus between women in CEO positions and eco-innovation? Based on our research questions, firm size is likely a determining factor in the GI of female CEOs. This research employs rigorous econometric modeling to analyze a substantial dataset of listed Asian industrial companies from 2013 to 2022. We have found a significant positive correlation between female CEOs and GI in Asian industrial firms. It has been proven that female CEOs in the industrial sector are more inclined to promote environmentally friendly practices. Furthermore, the size of an industrial firm amplifies the beneficial influence of a female CEO on the firm’s chances of engaging in GI initiatives. Regarding the moderating effect of size, the size of companies significantly magnifies the impact of female CEOs on GI. The effectiveness of female CEOs on environmentally friendly practices is more prominent in large corporations than in smaller ones. Our outcomes remain robust with respect to endogeneity issues using two-step GMM estimators. This study proposes that stakeholders, particularly in Asian countries, should promote the increased representation of females in CEO roles, particularly within large corporations. This is because women-led companies demonstrate superior performance in GI endeavors. Hence, regulators must establish policies that facilitate the participation of women in CEO positions within large-scale enterprises. These policies may strengthen the private sector’s capacity to foster sustainable innovation.