While prior research has recognized the significance of employees’ green innovative work behavior (GIWB) for organizational sustainability, few studies have explored how to effectively promote such behavior. Following the stimulus-organism-response (S-O-R) framework, we investigate how and when environmental corporate social responsibility (ECSR) drives employees’ GIWB. We conducted a two-wave lagged data analysis with 300 Chinese manufacturing employees. Our results reveal that creative self-efficacy and environmental commitment mediate the relationship between ECSR and employees’ GIWB. Additionally, we observe that person-organization (P-O) fit strengthens the indirect influence of ECSR on employees’ GIWB through creative self-efficacy. Conversely, P-O fit weakens the impact of ECSR on environmental commitment; however, it does not moderate the indirect influence of ECSR on employees’ GIWB through environmental commitment. These findings indicate that ECSR can effectively promote employees’ GIWB through multiple psychological mechanisms, and its impact varies depending on different levels of P-O fit. Our study offers novel theoretical insights and practical evidence to enhance employees’ GIWB, thereby contributing to sustainability in the Chinese manufacturing industry.