Enterprise green human resource management (GHRM) strives to foster harmonious development among employees and the environment and among employees and the organization, as well as between employees and stakeholders, by stimulating individuals' green behavior, thereby enhancing the sustainable development performance of the enterprise. Based on the questionnaire data of 452 large enterprises in Beijing, Shanghai and Wuhan, China, from September 2021 to July 2022, and based on the optimal distinctiveness theory and stakeholder theory, this article examined the mediation mechanism and boundary conditions between GHRM and sustainable development performance of enterprises from the perspective of organizational ambidexterity. The results showed that 1) GHRM positively affected organizational ambidexterity and sustainable development performance; 2) organizational ambidexterity mediated the relationship between GHRM and sustainable development performance; 3) responsible leadership moderated the direct effect of GHRM on organizational ambidexterity; and 4) responsible leadership moderated the indirect effect of GHRM on sustainable development performance through organizational ambidexterity. At the organizational level, this study reveals the impact mechanism of GHRM on sustainable development performance and determines the boundary conditions of the impact.