Objective: The current study examines the extent to which college students' reports of drinking to cope (DTC) with negative affect moderate the daily covariation between specific types of negative mood (sadness, fear, hostility, shyness and boredom) and alcohol use. Method: Participants were full-time college students, aged 18-20, attending a large Southeastern university (N = 72; 50% male). These individuals completed an experience-sampling protocol over a 1-month interval, to assess daily mood and alcohol use. Results: A series of Hierarchical General Linear Models found that individuals who reported low motives to cope through drinking showed an expected absence of daily mood and drinking covariation. For those reporting high coping motives, a complex and somewhat counterintuitive series of findings were found; students high in DTC drank less on days in which they experienced greater sadness. Analyses on the quadratic effects of mood revealed that when experiencing moderate to high levels of fear and shyness, individuals high in DTC were more likely to drink. For those low in coping motivations, fear and shyness did not predict daily drinking. Conclusions: Findings highlight the need to better our understanding of the exact meaning of DTC measures. In addition, there is a need to study how the context of college drinking influences self-medication and students' self-reports of DTC.