Given the crucial role of entrepreneurial optimism (EO) in prompting university students’ green entrepreneurial intentions (GEI), scholars are still striving to explore the causal mechanism that can facilitate the underlying relationship. Based on the social cognitive theory, we hypothesize that individual’s psychological resources, entrepreneurial resilience (ER) and entrepreneurial self-efficacy (ESE), mediate the association between EO and GEI. In addition, this study seeks to investigate the impact of sustainability orientation (SO) in the relationship between EO and GEI. Data for this study have been collected from Chinese university students in their final years. The authors used variance-based Structural Equation Modeling (SEM) to test the proposed hypotheses. The findings indicate that EO significantly influences GEI. Further, ER and ESE significantly mediate the link between EO and GEI. Moreover, this study finds that SO significantly moderates the relationship between EO and GEI such that the association is stronger at high levels of SO and vice versa. To the best of the authors’ knowledge, no prior studies have tested these relationships. The findings suggest that the proposed model can be utilized by practitioners and policy makers to facilitate the execution of green entrepreneurship among university students.