Emotion is presumed as a major reason for smoking, but this hypothesis needs support from data with high ecological validity. Regulatory emotional self-efficacy (RESE) is key for emotion regulation, therefore RESE is likely to moderate the relationship between emotional states and smoking. The present study used the ecological momentary assessment (EMA) to record the levels of pleasure,arousal, and smoking craving in 33 male current smokers抎aily lives, and examined the moderating effect of RESE in the rediction relationship between emotion and craving. The results showed that either end of the pleasure dimension, namely the high positive or high negative affect, predicted higher smoking craving. A similar pattern was also discovered in the arousal dimension, in which either of the activation and deactivation ends predicted higher smoking craving. Moreover, the prediction of negative affect on smoking craving was weakened by higher RESE, especially by the higher self-efficacy in managing negative emotions. In conclusion, smoking craving is closely related with immediate emotional states, and RESE reveals promising value in the reduction of smoking behavior. We discuss the possibility of expanding the RESE frame.