Virtual reality (VR) has shown promising results as an adjunct therapy for pain management. Recent literature exploring the use of VR for pain management among a chronic pain (CP) population has produced encouraging results, although little has been done to explore what about a VR intervention is the provider of the analgesic response. Furthermore, as has been suggested in the literature previously, little has been said of the association between pain tolerance and presence. This study primarily aimed to investigate pain tolerance differentiation between VR-head-mounted display (HMD) active and control interventions. Secondarily, this study looked to report on whether presence correlates to pain tolerance, among a CP population. A repeated-measures study design was used. Twelve participants received two 5-minute interventions while being subjected to experimentally induced pain. The interventions were as follows: (a) “active intervention,” an immersive and interactive experience (b) “control intervention,” and a nonimmersive controlled experience with no interaction. Tolerance to pain was assessed via the total time the participant continued the intervention. Presence was assessed via the Witmer and Singer's presence questionnaire. Participants also completed the Simulator Sickness Questionnaire, the Presence Questionnaire, and the Brief Pain Inventory. Pain tolerance was significantly higher in the active intervention compared with the control intervention (p = 0.005). There was a positive correlation between pain tolerance and presence during the active VR intervention. The media as opposed to the medium was determined to be responsible for greater tolerance to pain, as well as greater sense of presence, which was positively correlated to an increase in pain tolerance.