Engagement and attention are two crucial factors in determining the effectiveness of the learning experience, and both concepts have been studied extensively in educational sciences. However, these two aspects have not been studied sufficiently in eXtended Reality (XR) settings. Recognizing the growing role of XR in education, this review aims to study and understand this gap through a systematic literature review following the PRISMA methodology, renowned for its thoroughness and reliability. Our main objectives were to identify different methods to measure students’ attention and engagement and discuss strategies to enhance them. After a comprehensive analysis, we identified the most effective methods for measuring students’ engagement and attention in XR environments. Our study also makes evidence of the interest in an integrating evaluation approach gathering optimal tracking of attention and engagement during learning experiences. Finally, we discussed various approaches to enhance users’ engagement and attention, highlighting other relevant elements in designing and developing learning applications, such as the user-centred design of dedicated immersive paradigms and pedagogical-based learning scenarios.