Reversal theory constructs of playful and rebellious states are compared with negative affect as predictors of temptations and lapses and as predictors of three important correlates of resisting temptations to smoke: Cigarette availability, urge level, and coping during temptations. A total of 61 participants entered data in palmtop computers and tape recorders for the first 14 days of a cessation attempt. Multilevel, random-effects logistic regression analyses showed that fluctuations in playfulness, rebelliousness, negative affect, and cigarette availability all significantly discriminated temptations from nontemptations. Fluctuations in playfulness and rebelliousness, but not negative affect, significantly predicted being in situations where cigarettes were easily available. Fluctuations in playfulness, rebelliousness, and cigarette availability, but not urge levels or negative affect, significantly predicted coping during temptations, whereas coping, rebelliousness, cigarette availability, and urge levels predicted lapsing. Treatment and policy implications of these findings are discussed.