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 similar to those in real life; however, more research is needed to elucidate 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, which incorporated five social scenarios with three difficulty levels. 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 the 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. Planning ability substantially predicted performance in social scenarios, suggesting an implication in social skills. Immersive VR social skills training in individuals with ASD appears to be an appropriate service, but an errorless approach that is adaptive to the individual's needs should be preferred.