The COVID-19 pandemic has changed people’s lives, with the most prominent change being the use of Personal Protective Equipment (PPE). In this study, we used the extended Value-Identity-Personal (VIP) norm model to empirically analyze the influencing factors of Pro-Environmental Behavior (PEB) among college students in Xi 'an, China, while considering the usage of PPE as an example of PEB. We proposed nine hypothetical questions, and the VIP model was established through the SmartPLS software to test the valid questionnaires of 414 college students. The verification results indicated that all the nine hypotheses were supported statistically, with personal environmental social responsibility and personal norms showing the most significant direct impact on PEB; notably, personal norms were also strongly influenced by environmental personal social responsibility. Biosphere values affected PEB indirectly, through self-identity and individual norms. This study proposes viable countermeasures and suggestions for college students to improve PEB; our findings can serve as a reference for policymakers and stakeholders to ensure the effective waste management of personal safety equipment.