Although broad dispositional negative affect predicts problematic alcohol use, emerging evidence suggests that individual differences in how people experience and respond to negative affect may play an important role in risk. In a sample of 358 college students assessed twice across their first year of college, the current study investigated the predictive roles of trait negative affect, affective lability (the tendency to experience rapid and intense shifts in mood), negative urgency (the tendency to act rashly when highly emotional), and problem drinking via self-report measures completed online. Data were analyzed using structural equation modeling (SEM). Individual differences in how negative affect is experienced and responded to, represented by affective lability and negative urgency, predicted problem drinking above and beyond trait negative affect, and trait negative affect had no incremental predictive power. Additionally, affective lability predicted increases in negative urgency, but the opposite was not true. A focus on characteristic ways in which individuals experience and respond to negative affect, rather than negative affect itself, may improve risk assessment and clarify the etiology of problem drinking. Continued work toward the development of comprehensive affect-based risk models for problem drinking is needed.