This study applied Cognitive Experiential Self Theory to investigate the role of smoking expectancies and experiential associations with cigarette use in predicting smoking cessation in a sample of 155 Australian adults. Two discrete changes in the cessation process were investigated. The first involved a cognitive transition from not intending to quit smoking to intending to quit, and the second involved a behavioral transition from intending to quit to successful cessation. Multinomial logistic regression analyses suggested that experiential associations played no role in the transition from not intending to intending to quit, but moderated the effects of three types of smoking expectancies (negative consequences, positive reinforcement, and negative reinforcement) on the transition from intending to quit to successful cessation. The facilitative effects of smoking expectancies on cessation were substantially attenuated in participants who possessed more positive experiential associations with smoking.