This study empirically examines the relationship between CEO social capital and corporate ESG practices using a sample of A-share listed companies on the Shanghai and Shenzhen stock exchanges from 2009 to 2021. The research findings indicate that CEO social capital significantly enhances the level of corporate ESG practices, and the results are robust. Building upon this foundation, the study further reveals that CEO tenure and CEO overconfidence positively moderate the impact of CEO social capital on ESG practice levels. Furthermore, the additional research findings indicate that corporate ESG practices under the influence of CEO social capital contribute positively to enhancing the overall value of the firm. Our research results deepen the understanding in both academic and practical realms regarding the value creation function of CEO social capital. This provides empirical evidence for listed companies to recognize and leverage CEO social capital to enhance the level of sustainable development within the organization.