The integration of human-centric approaches has gained more attention recently due to more automated systems being introduced into our built environments (buildings, roads, vehicles, etc.), which requires a correct understanding of how humans perceive such systems and respond to them. This paper introduces an Immersive Virtual Environment-based method to evaluate the infrastructure design with psycho-physiological and behavioral responses from the vulnerable road users, especially for pedestrians. A case study of pedestrian mid-block crossings with three crossing infrastructure designs (painted crosswalk, crosswalk with flashing beacons, and a smartphone app for connected vehicles) are tested. Results from 51 participants indicate there are differences between the subjective and objective measurement. A higher subjective safety rating is reported for the flashing beacon design, while the psychophysiological and behavioral data indicate that the flashing beacon and smartphone app are similar in terms of crossing behaviors, eye tracking measurements, and heart rate. In addition, the smartphone app scenario appears to have a lower stress level as indicated by eye tracking data, although many participants don't have prior experience with it. Suggestions are made for the implementation of new technologies, which can increase public acceptance of new technologies and pedestrian safety in the future.