The purpose of this study was to examine among college students (N = 458; 249 women) whether drinking to cope (DTC) motives moderate the effect of daily negative mood states in predicting the onset of weekly drinking. Using a secure, Internet-based survey across 2 consecutive years, participants first completed measures of drinking motives and then reported on their mood states and alcohol use daily for 30 days. Multilevel discrete-time survival models indicated a significant interaction between DTC motives and anxiety in predicting the onset of drinking each week. As predicted, individuals with stronger DTC motives initiated drinking relatively earlier during high compared with low anxiety weeks. In contrast, individuals with weaker coping motives initiated drinking later during high compared with low anxiety weeks. We also found that coping motives moderated the association between anger and weekly drinking onset, with high DTC individuals showing later drinking onset on high anger weeks. Findings are discussed in terms of how time-to-drink models might inform us about the multiple processes involved in negative mood-related drinking, the importance of examining discrete negative mood states, and what strong endorsement of DTC motives might reflect among college students.