Human reaction plays a key role in improved protection upon emergent traffic situations with motor vehicles. Understanding the underlying behaviour mechanisms can combine active sensing system on feature caption and passive devices on injury mitigation for automated vehicles. The study aims to identify the distance-based safety boundary ("safety envelope") of vehicle-pedestrian conflicts via pedestrian active avoidance behaviour recorded in well-controlled, immersive virtual reality-based emergent traffic scenarios. Via physiological signal measurement and kinematics reconstruction of the complete sequence, we discovered the general perception-decision-action mechanisms under given external stimulus, and the resultant certain level of natural harm-avoidance action. Using vision as the main information source, 70% pedestrians managed to avoid the collision by adapting walking speeds and directions, consuming overall less "decision" time (0.17-0.24 s vs. 0.41 s) than the collision cases, after that, pedestrians need enough "execution" time (1.52-1.84 s) to take avoidance action. Safety envelopes were generated by combining the simultaneous interactions between the pedestrian and the vehicle. The present investigation on emergent reaction dynamics clears a way for realistic modelling of biomechanical behaviour, and preliminarily demonstrates the feasibility of incorporating in vivo pedestrian behaviour into engineering design which can facilitate improved, interactive on-board devices towards global optimal safety.