Psychological constructs, such as negative affect and substance use cravings that closely predict relapse, show substantial intra-individual day-to-day variability. This intra-individual variability of relevant psychological states combined with the “one day of a time” nature of sustained abstinence warrant a day-to-day investigation of substance use recovery. This study examines day-to-day associations among substance use cravings, negative affect, and tobacco use among 30 college students in 12-step recovery from drug and alcohol addictions. To account for individual variability in day-to-day process, it applies an idiographic approach. The sample of 20 males and 10 females (mean age = 21) was drawn from members of a collegiate recovery community at a large university. Data were collected with end-of-day data collections taking place over an average of 26.7 days. First-order vector autoregression models were fit to each individual predicting daily levels of substance use cravings, negative affect, and tobacco use from the same three variables one day prior. Individual model results demonstrated substantial inter-individual differences in intra-individual recovery process. Based on estimates from individual models, cluster analyses were used to group individuals into two homogeneous subgroups. Group comparisons demonstrate distinct patterns in the day-to-day associations among substance use cravings, negative affect, and tobacco use, suggesting the importance of idiographic approaches to recovery management and that the potential value of focusing on negative affect or tobacco use as prevention targets depends on idiosyncratic processes.