With technological advances, collection of intensive longitudinal data (ILD), such as ecological momentary assessments, becomes more widespread in prevention science. In ILD studies, researchers are often interested in the effects of time-varying covariates (TVCs) on a time-varying outcome to discover correlates and triggers of target behaviors (e.g., how momentary changes in affect relate to momentary smoking urges). Traditional analytical methods, however, impose important constraints, assuming a constant effect of the TVC on the outcome. In the current paper, we describe a time-varying effect model (TVEM) and its applications to data collected as part of a smoking-cessation study. Differentiating between groups of short-term successful quitters (N = 207) and relapsers (N = 40), we examine the effects of momentary negative affect and abstinence self-efficacy on the intensity of smoking urges in each subgroup in the 2 weeks following a quit attempt. Successful quitters demonstrated a rapid reduction in smoking urges over time, a gradual decoupling of the association between negative affect and smoking urges, and a consistently strong negative effect of self-efficacy on smoking urges. In comparison, relapsers exhibited a high level of smoking urges throughout the post-quit period, a time-varying and, generally, weak effect of self-efficacy on smoking urges, and a gradual reduction in the strength of the association between negative affect and smoking urges. Implications of these findings are discussed. The TVEM is made available to applied prevention researchers through a SAS macro.