Analyses of data from a random sample of 1,259 sexually active adolescents revealed that substance use was associated with increased sexual risk taking on 2 occasions of intercourse (1st intercourse ever and 1st intercourse with most recent partner), even after controlling for demographic experiential, and dispositional confounders. Within-persons analyses yielded similar results, indicating that adolescents who used substances, on 1 of the 2 occasions, reported higher levels of risk taking on the occasion when substances were used than on the no-substance use occasion. However, substance use was both more common and more strongly linked to risk taking among White than Black adolescents, suggesting that White adolescents are a greater risk of negative consequences related to substance use proximal to intercourse.