This article describes a multidimensional, multivariate, and multilevel approach to the assessment of nicotine withdrawal. In this prospective study, 70 adult smokers assigned to an active or placebo nicotine patch condition completed multiple daily assessments using an electronic diary. Average and individual growth curves were estimated for affective and nonaffective withdrawal symptoms. All symptoms but hunger increased significantly on the quit day and remained elevated for three weeks. Variability in symptom experiences across individuals increased from pre- to post-quit. Relations between symptom reports (e.g., negative affect or craving) and episodic events (e.g., stressful events or seeing someone smoke) changed from pre-quit to post-quit. Pre-quit increases in negative affect and quit-day increases in craving were inversely related to abstinence three months after the quit day, suggesting that anticipatory and immediate reactions to quitting influence success.