Decision-making in entrepreneurs is a key aspect of their skills, but much about these processes remains unexplained. During a Stroop task, concomitant N200, P300, and N450 eventrelated potentials were measured in 25 founder entrepreneurs and in age-matched and gendermatched nonfounders/nonentrepreneurs (NFNE). Reaction times were shorter among founder entrepreneurs. The N200 was shorter and N450 larger in founder entrepreneurs. The personalities of both groups were measured using the Temperament and Character Inventory-Revised. Founder entrepreneurs scored significantly higher in novelty-seeking and self-directedness dimensions, as well as in exploratory excitability, impulsiveness, optimism, eagerness, and responsibility subdimensions. Possible interactions among candidate variables to differentiate between founder entrepreneurs versus NFNE were also addressed, and the model including impulsivity, N450 latency, and impulsivity*N450 interaction came up as the best model for discrimination between founder entrepreneurs and NFNE. A shorter N200, mostly associated with bilateral supplementary motor area activation, revealed a faster capability to make decisions when information was noncongruent or blurred. However, the larger N450 revealed a more intense post-evaluation cognitive process happening in founder entrepreneurs and was accompanied by a greater activation of anterior frontal regions. The whole decision-making process consumed more time and resources in founder entrepreneurs, even if its closure was faster. Attention, memory, and alertness, among other factors, have been invoked to explain some of these differences. Founder entrepreneurs may have cognitive and heuristic differences compared with the general population.