The development of virtual reality (VR) in enhancing the effectiveness of the learning process, with its interactive, immersive, and intuitive pedagogical environment, has become a necessity for corporations with increasingly complex operations. However, VR users’ perceptions, openness and learning effectiveness are seldom comprehensively evaluated, particularly in learning complex industrial operations. In this study, grounded in the technology acceptance model, a moderated mediation model of perceived usefulness, ease of use, openness to experience, and engagement in VR-based learning was developed. The model was empirically validated using responses collected from 321 users who were trained on aircraft and cargo terminal operations powered by a novel VR-based learning platform. A survey to measure openness to experience and a pre-training performance test were carried out, followed by a post-training survey of learners’ intrinsic factors, including the influence of perceived usefulness, openness to experience, and attitude towards learning. The study revealed that learners with an open attitude towards experiencing new technology tend to perceive VR technology as a useful platform for training. In addition, the learners with more positive views of VR technology-supported training were more engaged in learning.