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People who drink alcohol to cope with negative affect tend to drink more and experience more frequent negative alcohol-related consequences. Experiential avoidance—the tendency to avoid, suppress, or otherwise attempt to control unwanted inner experiences—is a largely pathological process that may help account for how negative affect is linked to increased alcohol consumption. However, research to-date has typically used global, trait-like measures, which limit our understanding of the conditions under which experiential avoidance is problematic. The current study tested both between-person (trait) and within-person (daily) variation in experiential avoidance and negative affect as predictors of solitary and social drinking in a sample of 206 adult drinkers who completed daily diaries for 21 days. Participants higher in trait experiential avoidance drank alone more often, whereas those higher in trait negative affect consumed greater quantities when drinking alone. Although daily fluctuations in experiential avoidance did not predict solitary drinking, there was a significant interaction between daily experiential avoidance and trait negative affect. For participants high in trait negative affect, greater experiential avoidance on a given day predicted consuming more when drinking alone. For participants low in trait negative affect, greater experiential avoidance on a given day predicted drinking alone more often, but consuming fewer drinks on these occasions. Experiential avoidance did not predict social drinking in any model. Overall, results suggest that a broader tendency to experience negative affect sets the context for experiential avoidance to be linked to more harmful patterns of drinking.