There is consistent evidence that impulsivity-like traits relate to problematic alcohol involvement; however, identifying mechanisms that account for this relation remains an important area of research. Drinking refusal self-efficacy (or a person's ability to resist alcohol; DRSE) has been shown to predict alcohol use among college students and may be a relevant mediator of the impulsivity–alcohol relation. The current study examined the indirect effect of various constructs related to impulsivity (i.e., urgency, sensation seeking, and deficits in conscientiousness) via several facets of DRSE (i.e., social pressure, opportunistic, and emotional relief) on alcohol-related problems among a large sample of college students (N = 891). Overall, results indicated that certain DRSE facets were significant mediators of the relation between impulsivity-related constructs and alcohol problems. More specifically, emotional-relief DRSE was a mediator for the respective relations between urgency and deficits in conscientiousness and alcohol problems, whereas social-DRSE was a significant mediator of the respective relations between urgency and sensation seeking with alcohol problems. Results from this study suggest particular types of DRSE are important mediators of the relations between specific impulsivity constructs and alcohol-related problems. These findings support prevention and intervention efforts that seek to enhance drinking refusal self-efficacy skills of college students, particularly those high in certain personality features, in order to reduce alcohol-related problems among this population.