With the advent of the intelligence era, the empowerment of technology in education has triggered changes in the forms and concepts of teaching and learning. Virtual reality (VR), as a potential educational technology, has been widely used in teaching, providing students with almost real learning experiences. In particular, practice-centered pre-service teacher education is in greater need of VR. This case study applied and improved the Extended Unified Theory of Acceptance and Use of Technology (UTAUT2) as a theoretical foundation to explore pre-service teachers’ intention and behavior of adopting the VR training system. A sample of 278 Chinese pre-service teachers was collected by implementing the partial least squares structural equation modeling (PLS-SEM) via the Smart-PLS software. Study results reveal that pre-service teachers’ behavioral intention of adopting the VR training system is positively impacted by self-efficacy, effort expectancy, social influence, performance expectancy, facilitating conditions, and hedonic motivation, ranked from highest to lowest. Their use behavior with the training system is positively impacted by behavioral intention, facilitating conditions, and habit. Accordingly, this study presents suggestions for higher education institutions and VR education system developers on how to use and design VR training systems in pre-service teacher education through model construction, model validation, and conclusion analysis.