Understanding the ways different people perceive and apply acquired knowledge, especially when driving, is an important area of study. This study introduced a novel virtual reality (VR)-based driving system to determine the effects of neuro-cognitive load on learning transfer. In the experiment, easy and difficult routes were introduced to the participants, and the VR system is capable of recording eye-gaze, pupil dilation, heart rate, as well as driving performance data. So, the main purpose here is to apply multimodal data fusion, several machine learning algorithms, and strategic analytic methods to measure neurocognitive load for user classification. A total of ninety-eight (98) university students participated in the experiment, in which forty-nine (49) were male participants and forty-nine (49) were female participants. The results showed that data fusion methods achieved higher accuracy compared to other classification methods. These findings highlight the importance of physiological monitoring to measure mental workload during the process of learning transfer.