This study aims to explore the application of Virtual Reality (VR) in situated pedagogy and its subsequent impact on learners' behavioral beliefs. In the wake of rapid technological progression, VR technology has been extensively integrated into educational settings, thereby providing a more immersive learning milieu. Furthermore, the theory of situated teaching underscores the importance of amalgamating learning content with real-life scenarios to foster students' critical thinking and creativity. The role of the senses, serving as a primary conduit of information during the learning process, is crucial, even within virtual environments. Consequently, the study fabricates a virtual café scenario, facilitating learners to engage in a multisensory VR environment which includes the incorporation of olfactory sensor to augment the sense of immersion. Next, we propose the integrated model (depicted in Figure 1) of explicit (such as self-reporting and personal reflection) and implicit (such as EEG measurements) factors of learners' behavioral beliefs. Through laboratory experiment, we utilize Electroencephalography (EEG) technology (illustrated in Figure 2) to capture learners' real-time responses and "unconscious" behavioral processes during their interaction with the VR technology, rendering the overall learning behavior more transparent and comprehensible. Based on data collected from 70 participants so far, it has been found that multisensory learning, although it increases cognitive load and stress, enhances engagement and mental imagery, which in turn improves learning outcomes. If educators incorporate related technologies into their pedagogical practices, they can make adjustments and corrections based on these insights, thereby enhancing the learning efficacy of students.