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Slow‐releasing carbohydrates may delay the effects of fatigue after exhaustive exercise. The purpose of this study was to observe the influence that hydrothermally modified starches (HMS) and traditional maltodextrin (MAL) supplements had on physical endurance and mental performance following exhaustive exercise. Male participants completed a VO2 max and 2 days of cycling sessions using a Velotron ergometer. Cycling sessions were performed at 70% of the VO2 max workload for 150 min. Supplements were consumed 30 min before cycling and during exercise at the 120‐min mark (1 g CHO/kg body weight). Brain activity was measured using a Neuroscan 64‐channel electroencephalogram cap. Go‐no‐go and N‐back tasks were performed before and after cycling bouts. Blood glucose, lactate, ketones, and urine‐specific gravity were measured before, during, and after cycling. VO2 and rate of perceived exertion were recorded in 15‐min intervals. Ketones increased significantly more for HMS than MAL from pre‐ to postcycling measurements (p < 0.05). Reaction times for go‐no‐go and N‐back were faster for HMS postexercise. Event‐related potential differences were present in both mental tasks following exhaustive exercise. HMS supplementation decreased the impact of cognitive and physical fatigue postexercise.