Poor social skills in autism spectrum disorder (ASD) are associated with reduced independence in daily life. Current interventions for improving the social skills of individuals with ASD fail to represent the complexity of real-life social settings and situations. Virtual reality (VR) may facilitate social skills training in social environments and situations proximal to real life, however, more research is needed for elucidating aspects such as the acceptability, usability, and user experience of VR systems in ASD. Twenty-five participants with ASD attended a neuropsychological evaluation and three sessions of VR social skills training, incorporating 5 social scenarios with three difficulty levels for each. Participants reported high acceptability, system usability, and user experience. Significant correlations were observed between performance in social scenarios, self-reports, and executive functions. Working memory and planning ability were significant predictors of functionality level in ASD and the VR system’s perceived usability respectively. Yet, performance in social scenarios was the best predictor of usability, acceptability, and functionality level in ASD. Planning ability substantially predicted performance in social scenarios, postulating an implication in social skills. Immersive VR social skills training appears effective in individuals with ASD, yet an error-less approach, which is adaptive to the individual’s needs, should be preferred.