The current study examined the prospective relationship between distress tolerance (DT) and positive and negative cigarette smoking outcome expectancies, which are reliable predictors of the onset and maintenance of smoking behaviors. Data from a longitudinal study (N = 204) examining risk behaviors in adolescence were used to assess whether DT predicts individual differences in rate of change in smoking outcome expectancies over 4 annual assessment waves through adolescence. Adolescents (mean age at first wave: 13.03 years; SD = 0.88 years) completed a behavioral task assessing DT at baseline and a self-report measure of adolescent smoking expectancies annually across 4 years. Latent growth curve models were estimated to test our hypotheses. Results showed that DT at baseline did not significantly predict initial levels of negative affect reduction (NAR) expectancies, but NAR expectancies increased more quickly over time for adolescents with lower DT. Moreover, as hypothesized, DT did not prospectively predict significant changes in smoking expectancies outside of the domain of NAR, including negative physical feelings, negative social impression, and boredom reduction expectancies. These findings suggest that DT is a useful indicator of adolescent expectancies about the consequences of cigarette smoking, particularly those focused on reducing negative affect. Thus, DT may be an important target for preventing smoking initiation among adolescents via this putative mechanism. Theoretical and clinical implications are discussed within the context of observed effect sizes.