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The present study examined whether the tendency to experience negative affective states combines with smoking outcome expectancies to predict smoking behavior over time. Participants were 121 young adults and resource people recruited from 3 alcohol and drug treatment programs and through community advertisements. Each participant completed 3 interviews over a 4-year period. Results indicated that dispositional negative affect and positive smoking expectancies were significantly correlated with smoking behavior both within and across time. Expectations of positive and negative reinforcement partially mediated negative affect's relation with smoking across time. Positive expectancies did not function as a moderator of negative affect's relation with smoking behavior. These results represent an important step in incorporating smoking outcome expectancies into multivariate models of smoking risk.