Compared to other types of companies, family businesses tend to be more dominated by the traditional notion of familialism, believing that women should be more responsible for handling family affairs rather than being involved in business operations and decision-making. Yet there is still a controversy about whether female chairpersonship is more favorable to enterprise development than male chairpersonship. Driven by the globalization process and sustainable development strategies, ESG has become an important indicator for evaluating corporate sustainability and social responsibility. This paper empirically investigates the effect and mechanism of the gender of the chairperson on the ESG performance of family firms by using A-share family firms in China from 2009 to 2022 as the research sample. The results show that female chairpersonship significantly enhances the ESG performance of family firms, and this facilitating effect mainly focuses on the social and governance dimensions, and policy compliance is an important reason why female chairpersonship promotes the ESG performance of family firms. The study also finds that female chairpersons contribute more to family firms’ ESG performance in family firms whose chairpersons are from outside the family, those are indirectly founded, those with a high degree of ownership and control rights disparity, and those with single actual controller. This paper provides a framework for the study of the gender of chairpersons on the ESG performance of family firms, and also provides useful references for the professional equality between males and females and the selection of chairpersons in the real economy.