The current study examines a paradox in the college student alcohol use literature where drinking to cope with negative affect (DTC) is concurrently and prospectively linked to problems with alcohol; however, experience sampling and daily diary studies have either failed to find a link between affect and drinking within a day, or found the relationship only under specific circumstances. Participants were 124 college students from a large Southeastern university. These individuals completed an online daily diary protocol for two weeks to report daily emotions, drinking motives and alcohol consumption. A series of HGLM analyses were conducted to test study hypotheses. The influence of self-awareness on the moderating effects of dispositional DTC on mood-drinking covariation were considered in two separate models, for global negative affect using the DTC subscale of Cooper's drinking motives questionnaire (1994) and also for sadness using a sadness specific measure of DTC. Neither the standard dispositional DTC model nor the dispositional sadness specific models were significant. DTC was also assessed as a daily process. The moderating effects of global negative affect and sadness specific daily drinking motives on mood-drinking covariation on drinking days was tested and a significant interaction between daily sadness motives, sad mood, and quantity of alcohol consumed was found. At relatively higher levels of daily sadness DTC individuals drank more when experiencing more sad mood and drank less when experiencing less sad mood, whereas those relatively low in DTC drank less on days with more sad mood and drank more on days with less sad mood. The global negative affect model was not supported. Post-hoc analyses were conducted to examine potential methodological explanations for the lack of findings in the three of the four models tested. Strengths, limitations, clinical implications and future directions are discussed.