Against the backdrop of the coordinated promotion of high-quality economic development and ecological civilization construction in China, environmental pollution has emerged as a focal issue in the pursuit of sustainable development. Enterprises, as the mainstay of market economic development and a significant source of environmental problems, play a crucial role in China’s journey towards achieving the dual carbon goals. Employees, as the participants and implementers of corporate operations, have behaviors that directly influence the realization of a company’s environmental performance. Consequently, there is growing attention and heightened importance placed on how to effectively motivate employees’ green behaviors. Based on the affective events theory, and building upon a systematic review of the concepts of responsible leadership and employees’ green behaviors, as well as past research findings, this study commences from the perspective of responsible leadership. By introducing two mediating variables, namely green human resource management and environmental responsibility, a chain mediating model is developed to probe into the mechanism through which responsible leadership impacts employees’ green behaviors. A key aspect of this exploration is to spotlight the mediating roles of green human resource management and environmental responsibility, thereby adding to the research on the determinants of green human resource management. Through a questionnaire survey, data were collected from manufacturing enterprises in regions such as Sichuan and Jiangsu. Structural equation modeling was employed for empirical analysis to test the research hypotheses and theoretical model. The results reveal that there is a significantly positive impact of responsible leadership on employees’ green behaviors. It suggests that responsible leadership can efficiently prompt employees’ green behaviors, and this, in turn, is beneficial for enterprises in reaching their environmental performance targets. Green human resource management serves as a mediator between responsible leadership and employees’ green behaviors. Similarly, environmental responsibility functions as a mediator in the relationship between responsible leadership and employees’ green behaviors. Responsible leadership indirectly influences employees’ environmental behaviors through the sequential transmission paths of green human resource management practices and environmental responsibility, exhibiting a chain mediating effect. Among these three paths, the mediating effect of green human resource management is the strongest. In the heterogeneity analysis, it is found that, compared with female employees, the impact of responsible leadership on employees’ green behaviors is more significant among male employees. When compared with enterprises in central and western regions, the impact of responsible leadership on employees’ green behaviors is more pronounced in enterprises in the eastern region. The management implications of the conclusions of this article are as follows: For enterprises, they should continuously improve green human resource management measures. Enterprises in the eastern region should leverage their economic foundation to create environmental protection practice cases. Enterprises in the central and western regions should strengthen industry-university-research cooperation and introduce advanced green technologies and management experience. For leaders, this study reveals the promoting effect of responsible leadership on employees’ green behaviors. Leaders should systematically convey the concept of corporate sustainable development to organizational members, integrate environmental protection values into daily management communication, consciously cultivate a team environmental protection culture, establish social norms that support green behaviors, and combine emotional identification with value internalization to motivate employees’ spontaneous environmental behaviors. For employees, they should take the initiative to enhance the level of environmental protection awareness, actively participate in sustainable development practices, and recognize and implement the enterprise’s green management concepts and related institutional arrangements, so as to support the healthy and sustainable development of the enterprise. Only through the coordinated efforts of enterprises, leaders, and employees can the realization of sustainable development goals be more effectively promoted.