A review of the literature shows that much academic effort has been expended studying information system usage and information technology adoption. However, these theories/models based on psychological research are not specific to the virtual reality context and may not fully capture the nature of virtual reality-based learning system (VR-BLS) usage behavior in the virtual environment. Given the limited utility of existing theories/models, this study aims to build a theoretical model and to validate the psychological and physiological effects of using VR-BLSs. To explore students' usage intentions, this study integrates the extended unified theory of acceptance and use of technology (UTAUT2), representing the psychological effects, and the perceived physiological vulnerability to IT usage (PPVITU), representing the physiological effects. We empirically examine the research model using a cross-sectional survey, collecting data from a sample of 352 students, and utilizing partial least squares (PLS) for the analysis. Our findings show that the behavioral intention to use VR-BLSs is determined by performance expectancy, social influence, and facilitating conditions. Moreover, PPVITU negatively moderates the association between social influence and the behavioral intention to use VR-BLSs. The results of this study enhance our understanding of the relationship between students' VR-BLS usage behavior and VR-based education.