This study examines the attributes of virtual reality (VR) technology to delineate three fundamental dimensions of digital experience in online education: virtual reality scenes, virtual character-led teaching, and virtual reality games. Data were collected through a questionnaire administered to 405 individuals with prior VR experience, and structural equation modelling (SEM) was utilised to analyse the relationship between digital experience and purchasing behaviour. The findings indicate that each of the three dimensions of digital experience exhibits a significant and positive correlation with purchase intention, with instruction led by virtual characters exerting the greatest influence. Furthermore, the moderating variable—emotional state—demonstrates that positive emotions amplify the impact of digital experience on purchase intention. These results contribute valuable theoretical insights for users, expand the understanding of digital experiences in online education, and offer practical recommendations for the design of VR-enhanced courses and VR-driven marketing strategies.