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Childhood aggression is a known risk factor for adolescent substance use; however, aggression is a complex construct, and developmental researchers have identified a variety of subdimensions that may be germane to substance use. Very little research has examined risk pathways from subdimensions of aggression. The current study examined a developmental model and tested whether childhood proactive aggression, reactive aggression, or both were related to the development of substance use in adolescence in a sample of 126 children (mean age at initial assessment = 10.4 years, SD = 0.51). Peer rejection and peer delinquency were examined as potential mediators of these relations. The findings suggest that proactive aggression was indirectly associated with substance use through peer delinquency. Reactive aggression was also indirectly associated with substance use through a complex mediational chain, such that high levels of reactive aggression were associated with high levels of peer rejection, which in turn were associated with peer delinquency (p = .06), which subsequently predicted substance use.