Crucial elements for police firearms training include mastering very specific psychophysiological responses associated with controlled breathing while shooting. Under high-stress situations, the shooter is affected by responses of the sympathetic nervous system that can impact respiration. This research focuses on how frontal oscillatory brainwaves and cardiovascular responses of trained police officers (N = 10) are affected during a virtual reality (VR) firearms training routine. We present data from an experimental study wherein shooters were interacting in a VR-based training simulator designed to elicit psychophysiological changes under easy, moderate and frustrating difficulties. Outcome measures in this experiment include electroencephalographic and heart rate variability (HRV) parameters, as well as performance metrics from the VR simulator. Results revealed that specific frontal areas of the brain elicited different responses during resting states when compared with active shooting in the VR simulator. Moreover, sympathetic signatures were found in the HRV parameters (both time and frequency) reflecting similar differences. Based on the experimental findings, we propose a psychophysiological model to aid the design of a biocybernetic adaptation layer that creates real-time modulations in simulation difficulty based on targeted physiological responses.