The construct of self-efficacy, which is assessed either in confidence- or temptation-related instruments, presumably predicts transitions between the transtheoretical model stages of change and ultimately smoking cessation outcome. To elucidate its predictive potential for smoking cessation in a general care setting, we examined the association of baseline scores of the situational temptations inventory with month 12 smoking status in 577 heavy smokers participating in a cluster-randomized study of physician training and financial incentives for smoking cessation in Germany. At follow-up, abstinence could be validated in 56 patients. The temptation sub- and total scores were not bivariately associated with altered odds of smoking cessation, in contrast to established predictors like the Fagerstrom test of nicotine dependence and the stages of change. They were associated with the Fagerstrom scores, but not with the stages of change. Controlling for both cessation predictors, in particular the positive/social temptation subscore was associated with quitting. Additional studies are needed to fully understand how situational temptations relate to smoking cessation outcomes and explain variance beyond that of more established predictors of cessation.