This study examines the relationship among the employees–organization pro-environmental values fit, supervisors’ PEVs and employees’ pro-environmental behaviors. Informed by the PEB, organizational values and employee–organization fit literature, we propose and test hypotheses that under egoistic, altruistic and biosphere-value orientations, E–O PEVs fit versus non-fit have significant effects on employees’ private-sphere PEB and public-sphere PEB, identifying supervisors’ PEVs as a moderator. An empirical investigation indicates that the effect of E–O PEVs fit on employees’ private-sphere PEB and public-sphere PEB varies as the (...) value orientation differs. More specifically, under the context of altruistic and biosphere-value orientations, if the organizational PEVs do not match the employees’ PEVs, especially when the former exceeds the latter, employees’ PEB will rise as the organizational PEVs increase. As for egoistic value orientation, when organizational PEVs exceed employees’ PEVs, not only will public-sphere PEB stop decreasing and tend to stabilize, but also private-sphere PEB will rise to a slight degree. Furthermore, compared with altruistic and biospheric values dimensions, supervisors who promote egoistic PEVs will have a more significant effect on the relationship between global E–O PEVs fit and employees’ PEB. Finally, we suggest that the goals of an organization and its supervisors need to be combined within the actual situation of Chinese corporations to truly implement corporate green practices by balancing the profit goal and the environmental goal. (shrink)