Despite the rising interest in corporate environmental policy (CEP), our understanding of the underlying mechanisms linking CEP to employee positive or negative behavior, and the circumstances in which both relationships are magnified or attenuated is still incomplete. Adopting the conservation of resources (COR) theory and self-determination theory (SDT), we develop a multilevel model of employee green and non-green behaviors, explaining why and when CEP leads some employees to actively embrace green activities and others to resist doing so or engage in non-green behavior. Using two-wave data from a large-scale survey, we test a moderated mediation model in which CEP positively affects employee green self-efficacy and role overload, resulting in the increased green and non-green behaviors, respectively. Besides, we find that autonomous motivation strengthens the indirect effect of CEP on employee green behavior through green self-efficacy, and controlled motivation reinforces the impact of CEP on employee non-green behavior by increasing their perception of role overload. Our findings contribute to a more balanced understanding on the double-edged sword effect of CEP by revealing its benefits and detriments and shedding light on the psychological mechanisms and contextual conditions that foster or impede how CEP is indirectly translated into employee green behavior. We also discuss ethical and practical implications for promoting environmental policies and initiatives, providing preliminary evidence for CEP’s potential downside that may induce employee counterproductive behavior.