Abstract: Based on the integrated model of emotion and cognition on pro-environmental behavior, the current study is conducted in order to deeply understand the intrinsic influential mechanism of nature connection (NC) to pro-environmental behavior (PEB), within which we assume that empathy with nature (EN) plays as a mediator and relative value orientation (RVO) plays as a moderator. Results showed that NC positively predicted pro-environmental intention, EN played a mediating role, and RVO moderated the impact of NC on EN. Compared with individuals who prefer money, individuals who prefer environment had a larger difference on EN between high and low NC. However, neither NC nor EN had a significant correlation with environmental decision-making. The present study provides a new proof for the integrated model of emotion and cognition on PEB, offering empirical evidence to the gap between intention and behavior found in pro-environmental studies. The findings of this study can also provide recommendations for environmental protection awareness-raising efforts. Follow-up research needs to further explore the differences between the influence of pro-environmental intentions and behaviors.