Immersive virtual reality (IVR) and Metaverse applications are gaining attention in the educational field, showing potentials in transforming traditional learning methods by supporting active and experiential forms of learning. Our study, conducted within the context of an Italian university course, employs the Extended Expectation-Confirmation Model (EECM) as a theoretical framework to explore the key aspects of students’ acceptance and continued intention to use IVR and Metaverse integrated learning environments in educational settings. The EECM, which bridges the gap between pre-adoption expectations and post-adoption experiences, provides a comprehensive perspective for exploring technology adoption in education. Students’ attitudes were assessed before and after they completed an elective course offered by the university that delved into IVR and Metaverse applications. During the course, students explored the theoretical and practical applications of these technologies, engaging in a variety of experiences, from immersive relaxation exercises to immersive educational platforms in the emerging Metaverse. Contrary to common assumptions, pre-adoption factors like performance and effort expectancy had limited impact on expectancy confirmation. However, when students’ initial expectations matched their experiences, their perceptions of the technology’s usefulness, satisfaction, and confidence in its use were positively enhanced, influencing their continued intention to integrate these tools in education.