The importance of employee green behavior (EGB) to an enterprise’s green development goal is increasingly emphasized in many industries. However, to date promoting EGB through interaction, namely between individuals and organizations, has not been a central concern. Therefore, from the perspective of the person-organization fit, this study considers the psychological distance between employees and the organization as a moderating variable, exploring the mechanisms of values fit, needs-supplies fit, and demands-abilities fit on green behaviors as within and outside the scope of employee responsibility. After collecting the results of questionnaires from 412 employees, our hypotheses were tested using the Structural Equation Model (SEM). The results show that (1) person-organization fit can effectively promote EGB in the workplace. However, different types of person-organization fit have different influencing paths and effect-strengths on employees’ task-related green behavior and proactive green behavior. (2) Values fit has the greatest incentive effect on EGB, followed by demands-abilities fit, while needs-supplies fit promotes only eco-helping behavior. (3) Psychological distance has a significant moderating effect on the relationship between the person-organization fit and EGB. The effect of person-organization fit on EGB is enhanced when employees are close with less emotional distance, while the effect is weakened in the case of close expectation distance. Finally, this study provides suggestions for enterprise managers providing ways to motivate EGB through the selection and allocation of human resources.