The purpose of this research was to examine how affective associations with smoking and outcome expectancies regarding smoking are related to smoking status and intention to quit among smokers. Researchers and practitioners can draw on findings regarding affective associations and outcome expectancies to provide a further basis for smoking prevention and intervention efforts. Four-hundred and one participants, half of whom were current smokers, from the United States and Australia completed measures of affective associations with smoking and outcome expectancies relating to smoking. Current smokers also indicated their readiness to quit. Participants with more positive affective associations were more likely to be smokers. Current smokers with more positive affective associations expressed less readiness to quit smoking. Outcome expectancies regarding reinforcement stemming from smoking and consequences stemming from smoking were related to smoking status and intention to quit. Outcome expectancies related to smoking significantly mediated the relationship between affective associations and smoking status. Among smokers, outcome expectancies related to smoking significantly mediated the relationship between affective associations and readiness to quit. Implications for prevention and intervention programs are discussed.