The recent interest in the use of Immersive Virtual Reality (IVR) in education seems to correspond with the increased affordability, accessibility and functionality of IVR hardware and software. IVR has the potential to enhance immersion, improve spatial capabilities, promote empathy, increase motivation and possibly improve learning outcomes. However, the extent to which teachers capitalise on these potentials in the future depends their perceptions of IVR and their behavioural intentions to use it. Accordingly, this study aimed to identify relevant factors and influences relating to preservice teachers’ behavioural intention to use IVR, using the Unified Theory of Acceptance and Use of Technology 2 (UTAUT2) model. Confirmatory factor analysis revealed that UTAUT2 provided a suitable model to describe preservice teachers’ perceptions of IVR on all dimensions (performance expectancy, effort expectancy, social influence, facilitating conditions, hedonic motivation, price value, habit and behavioural intention), with hedonic motivation receiving the highest scores and habit scoring the lowest. Interview responses revealed the reasons for the substantial variation in preservice teacher perceptions, which depended on a range of external- (“first-order”), internal- (“second-order”) and design (“third-order”)-related issues. Implications for schools, educational leaders and teacher education are discussed.