Virtual reality (VR) games construct an immersive context for the youth’s entertainment and learning. VR game addiction (VAD) occurs simultaneously and brings about psychological issues. The current research employed a maximum likelihood estimation method to construct a structural equation model, by which learners’ VR consumption behaviors were examined. The bootstrapping approach was adopted to explore further the mediation of VR realism (VRR) and the moderation of VR affordance on learners’ VAD, which potentially leads to distressing behavioral and psychological circumstances. Data were collected from 575 students recruited in the survey, which was followed by a test of reliability and validity through confirmative factor analysis. Results concluded that VRR and consumers’ cognitive satisfaction played a significant role as mediators while conceptualizing addictive behavior based on VR-perceived experience of consumers, self-efficacy, and interactivity. Moreover, this study conceptualized addictive behavior toward VR games through a structural equation model in a media-rich environment and suggested practical implications to reduce addictive behavior.