This study tested a path model in a sample of young adults ( n = 402) linking positive and negative affect to alcohol consumption and problems, via enhancement and coping motives respectively. Motivational models of alcohol use suggest that individuals drink in order to alleviate themselves from negative affective states or to enhance positive moods or feelings (Cox & Klinger, 1988). Deficits in modulating attention toward emotional experience (i.e., involuntary attention to emotion - IAE; (Huang, Berenbaum, & Chow, 2013) and poor distress tolerance (Simons & Gaher, 2005) may contribute to maladaptive patterns of substance use (i.e., negative reinforcement). As negative affect increases, those with deficits in the ability to efficiently attend to emotions as well as the inability to withstand distress may seek more external means of regulating unwanted or intrusive emotional experiences via alcohol. Coping motives were directly associated with alcohol-related problems, while enhancement motives were directly associated with problems both directly, and indirectly via alcohol consumption. The hypothesized interaction between positive affect and IAE was insignificant. However, the interaction between negative affect and IAE to coping motives was conditional upon levels of distress tolerance, with the moderating effect of involuntary attention being significant at high but not low levels of distress tolerance. Distress tolerance exhibited direct, inverse, associations with alcohol-related problems. This pathway was significant over and above the direct effects of both coping motives and alcohol consumption. This suggests that while tolerance for emotional distress may reduce negative reinforcement drinking, it also fosters adaptive regulation when intoxicated.