Although social anxiety is related to smoking and nicotine dependence, few researchers have sought to identify factors that contribute to these relations. The current study examined whether social anxiety was associated with cognitive vulnerability factors related to smoking: perceived barriers for quitting, cessation-related problems, negative-affect-reduction-outcome expectancies, and negative-affect-reduction motives. Further, we tested whether social anxiety was robustly related to these factors after controlling for cigarettes smoked per day, gender, alcohol-use frequency, lifetime cannabis-use status, panic attack frequency, anxiety sensitivity, and negative affectivity. The sample consisted of 580 (38.6% female) treatment-seeking smokers. Social anxiety was associated with perceived barriers for quitting, cessation-related problems, negative-affect-reduction-outcome expectancies, and negative-affect-reduction motives. After controlling for covariates, social anxiety was robustly related to perceived barriers for quitting, cessation-related problems, and negative-affect-reduction-outcome expectancies. Social anxiety was robustly related to negative-affect-reduction motives among men, but not women. Results indicate that social anxiety is robustly related to cognitive vulnerability factors associated with poorer cessation outcomes, suggesting that social anxiety may be an important therapeutic target during smoking cessation.