Empirical evidence suggests that mindfulness, psychological flexibility, and addiction are interrelated in decision making. In our study, we investigated the relationship of the behavioral profile, composed of mindfulness and psychological flexibility, and smoking status on delay and probability discounting. We demonstrated the interaction of the behavioral profile of mindfulness and psychological flexibility (lower or higher) and smoking status on delay discounting. We found that individuals who smoked and displayed higher mindfulness and psychological flexibility devalued rewards at a slower rate, compared to smokers with a lower profile. Importantly, in those with a higher profile, smokers discounted rewards no differently than nonsmokers. Smokers with a lower profile did display, however, increased impulsivity, compared to nonsmokers. These results suggest that behavioral interventions aiming to modify the behavioral profile with regard to mindfulness and psychological flexibility can indeed support the regulation of elevated impulsivity in smokers to equate with that of nonsmokers. In probability discounting, we observed that individuals with a higher profile displayed lower discounting rates, i.e., were less risk-averse, with no other significant main effect or interaction.