This study examined the psychometric properties of the Greek version of the Smoking Efficacy Scale (SES) for adolescents in a sample of 536 high school students. The factorial structure of the SES was examined by means of a series of exploratory factor analyses. The structural validity, the internal consistency, the temporal stability, and the concurrent validity of the SES were assessed. Exploratory and confirmatory factor analyses revealed a clear three-factor (emotion, opportunity, and friends) structure. Furthermore, SES predicted students’ smoking behavior. Overall, the multidimensionality of the SES was supported by our findings, suggesting that the Greek version of the SES appears to be a psychometrically sound instrument that can be used for the evaluation of smoking prevention and smoking cessation programs for high school students.