Objective: The current study examined the relationship between personality traits and baseline neuropsychological performance in college athletes. Method: 349 collegiate athletes (264 male, 85 female) were administered baseline neuropsychological batteries. Tests included: ImPACT, BVMT-R, HVLT-R, SDMT, Comprehensive Trail Making Test, Vigil/W CPT, Stroop, Digit Span, and the NEO-Five Factor Inventory (NEO-FFI). Given hypothesized differences between the personality trait extremes, high/low groups were established according to those who fell 1S.D. from the baseline mean. Total Battery (TB), Memory, Basic Attention (BA), and Complex Attention (CA) composites were established by summing baseline z-scores of associated indices. Results: Correlations between testing composites and personality factors revealed several significant correlations with small effects (r2 = 0.02–0.04). Effects increased when examining the high/low groups of significantly correlated factors (r2 = 0.03–0.18). Athletes with high Openness (t(103) = −4.93, p < 0.01), agreeableness (t(123) = −2.35, p < 0.05), and conscientiousness (t(102) = −2.11, p < 0.05) showed better TB performance. Those with high Openness had better memory performance (t(90) = −2.13, p < 0.05). Those with high Extraversion (t(103) = −2.65, p < 0.01) and high Conscientiousness (t(89) = −2.46, p < 0.05) showed stronger BA performance, while those with low Neuroticism (t(99) = −2.49, p < 0.05) and high Conscientiousness (t(102) = −2.88, p < 0.01) had stronger CA performance. Conclusions: Personality traits were associated with baseline neuropsychological performance in college athletes, with small-to-moderate effect sizes. Those falling in the extremes of the five traits showed the strongest correlations. Consideration of personality traits could inform assessment of sports-related concussion.