This study evaluated the impact of rapid heat stress on prefrontal cortex (PFC) oxygenation and hemodynamics. Previous work has demonstrated that heat stress affects cerebral oxygenation and hemodynamics. Fourteen male subjects performed a graded exercise test to a termination criterion (volitional maximum, core temperature = 39.5 °C, or a 2-hour time cap) with (GEAR) and without (NOGEAR) firefighting gear in a laboratory with an ambient temperature of 25–26 °C. Changes in oxyhemoglobin (O2Hb), total hemoglobin (tHb), and tissue oxygen saturation index (TSI %) were monitored in the left and right PFC using near-infrared spectroscopy (NIRS). Significant NIRS results were a plateau in the left-side O2Hb and tHb at 80 % of the time to termination (TTT) in NOGEAR, and 60 % of TTT in GEAR. These TTT points were when the subject’s core temperature (Tc) was equal to 38 °C. Additionally, there was higher left-side PFC activation during GEAR, as indicated by a significant decrease in TSI % from start to end of exercise and double the reduction in TSI % per minute in PPE compared to NOGEAR. There were no significant differences during the NOGEAR session. These data suggest that a rapid heat stress scenario (GEAR) causes altered cerebral oxygenation and hemodynamic response in the left-side PFC. The left PFC could be working harder to prevent fatigue in GEAR. This could affect cognitive processes during or following exercise in the heat while wearing personal protective equipment. Our results also support previous research demonstrating that NIRS is a sensitive metric of fatigue.