Young adulthood is a peak period for externalizing behaviors such as substance abuse and antisocial conduct. Evidence from developmental neuroscience suggests that externalizing conduct within this time period may be associated with a "developmental asymmetry" characterized by an early peak in sensation seeking combined with a relatively immature impulse control system. Trait measures of impulsivity-sensation seeking and premeditation-are psychological manifestations of these respective systems, and multiple prior studies suggest that high sensation seeking and low premeditation independently confer risk for distinct forms of externalizing behaviors. The goal of the present study was to test this developmental asymmetry hypothesis, examining whether trait premeditation moderates the effect of sensation seeking on substance use and problems, aggression, and rule-breaking behavior. Using a cross-sectional sample of college-enrolled adults (n = 491), we applied zero-inflated modeling strategies to examine the likelihood and level of risky externalizing behaviors. Results indicated that lower premeditation enhanced the effect of higher sensation seeking on higher levels of positive and negative alcohol consequences, more frequent drug use, and more problematic drug use, but was unrelated to individual differences in antisocial behaviors. Our findings indicate that the developmental asymmetry between sensation seeking and a lack of premeditation is a risk factor for individual differences in problematic substance use among young adults, and may be less applicable for antisocial behaviors among high functioning individuals.