Immersive virtual reality technology has been widely used in teaching and learning scenarios because of its unique visual and interactive experiences that bring learners a sense of immersive reality. However, how to better apply immersive virtual reality technology to learning environments to promote learning effectiveness is a direction that has been studied and explored by many scholars. Although a growing number of studies have concluded that immersive virtual reality technology can enhance learners’ attention in teaching and learning, few studies have directly linked both learning behaviors and attention to investigate the differences in behavioral performance across attention. In this study, attention data monitored by EEG physiological brainwaves and a large number of videos recorded during learning were used to explore the differences in the sequence of high attention behaviors across performance levels in an immersive virtual reality environment using behavioral data mining techniques. The results found that there was a strong correlation between attention and performance in immersive virtual reality, that thinking and looking may be more conducive to learners’ concentration, and that high concentration behaviors in the high-performing group accompanied the test and appeared after the monitoring, while the action continued to be repeated after the high concentration behaviors in the low-performing group. Based on this, this study provides a reference method for the analysis of the learning process in this environment, and provides a theoretical basis and practical guidance for the improvement of participants’ attention and learning effectiveness.