Risk taking (RT) measurement constitutes a challenge for researchers and practitioners and has been addressed from different perspectives. Personality traits and temperamental aspects such as sensation seeking and impulsivity influence the individual’s approach to RT, prompting risk-seeking or risk-aversion behaviors. Virtual reality has emerged as a suitable tool for RT measurement, since it enables the exposure of a person to realistic risks, allowing embodied interactions, the application of stealth assessment techniques and physiological real-time measurement. In this article, we present the assessment on decision making in risk environments (AEMIN) tool, as an enhanced version of the spheres and shield maze task, a previous tool developed by the authors. The main aim of this article is to study whether it is possible is to discriminate participants with high versus low scores in the measures of personality, sensation seeking and impulsivity, through their behaviors and physiological responses during playing AEMIN. Applying machine learning methods to the dataset we explored: (a) if through these data it is possible to discriminate between the two populations in each variable; and (b) which parameters better discriminate between the two populations in each variable. The results support the use of AEMIN as an ecological assessment tool to measure RT, since it brings to light behaviors that allow to classify the subjects into high/low risk-related psychological constructs. Regarding physiological measures, galvanic skin response seems to be less salient in prediction models.