This study investigated the effectiveness of head cooling on cognitive performance after 30 min and 60 min of running in the heat. Ten moderately-trained, non-heat-acclimated, male endurance athletes (mean age: 22 ± 6.6 y; height: 1.78 ± 0.10 m; body-mass: 75.7 ± 15.6 kg; VO2peak: 51.6 ± 4.31 mL-1>kg-1>min) volunteered for this study. Participants performed two experimental trials: head cooling versus no-cooling (within-subjects factor with trial order randomized). For each trial, participants wore a head-cooling cap for 15 min with the cap either cooled to 0°C (HC) or not cooled (22°C; CON). Participants then completed 2 × 30 min running efforts on a treadmill at 70% VO2peak in hot conditions (35°C, 70% relative humidity), with a 10 min rest between efforts. Working memory was assessed using an operation span (OSPAN) task immediately prior to the 15 min cooling/no-cooling period (22°C, 35% RH) and again after 30 min and 60 min of running in the heat. Numerous physiological variables, including gastrointestinal core temperature (Tc) were assessed over the protocol. Scores for OSPAN were similar between trials, with no interaction effect or main effects for time and trial found (p = 0.58, p = 0.67, p = 0.54, respectively). Forehead temperature following precooling was lower in HC (32.4 ± 1.6°C) compared with CON (34.5 ± 1.1°C) (p = 0.01), however, no differences were seen in Tc, skin temperature, heart rate and ratings of perceived exertion between HC and CON trials at any time point assessed (p > 0.05). In conclusion, despite HC reducing forehead temperature prior to exercise, it did not significantly improve cognitive performance during (half-time break) or after subsequent exercise in hot environmental conditions, compared to a no cooling control.