This investigation examined mediators of the longitudinal relation between negative affectivity and the development of problematic drinking behavior in adolescent boys and girls. In the present study, 499 early adolescents completed inventories of negative affectivity, attitudes toward delinquency, personal delinquency, and affiliation with delinquent peers. Positive attitudes toward delinquency emerged as the most consistent mediator and strongly predicted drinking frequency in various situations. Compared with personal delinquency, both attitudes toward delinquency and peer delinquency were superior predictors of affect-related drinking. Our results also demonstrated that positive attitudes toward delinquency mediated the relation between negative affectivity and later development of an alcohol use disorder. These findings suggest that a proneness to unpleasant affect impacts adolescent drinking by heightening risk for general rejection of normative behavior, rather than by increasing drinking as a means of managing affect. The importance and implications of testing delinquency variables together in the same model are discussed.