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Although emerging research suggests that pain-related anxiety may play a role in the maintenance of tobacco dependence, no previous work has examined pain-related anxiety as a predictor of smoking cessation outcomes. The current study aimed to test the hypothesis that pain-related anxiety would predict early lapse and relapse to cigarette smoking. These data were collected in the context of a primary study examining the role of emotional vulnerabilities in smoking cessation. The current analyses were conducted among 55 daily cigarette smokers who attempted to quit without psychosocial or pharmacological cessation aids. Pain-related anxiety was assessed at baseline using the Pain Anxiety Symptom Scale-20 (PASS-20). Early lapse and relapse were assessed using timeline follow-back procedures. Cox regression analyses indicated that pain-related anxiety was a significant predictor of both early smoking lapse and relapse such that for every 1-point increase on the PASS-20, the risk of early lapse increased by 3.7% and the risk of early relapse increased by 3.6%. These effects were evident above and beyond the variance accounted for by tobacco dependence, past 4-week pain severity, anxiety sensitivity, and the presence of current Axis I psychopathology. Kaplan-Meier survival analyses further revealed that among early lapsers, greater pain-related anxiety predicted a more rapid trajectory to lapse. Pain-related anxiety was also a significant predictor of early lapse when the sample was limited to smokers with past 4-week pain. These findings lend empirical support to the notion that pain-related anxiety may contribute to the maintenance of tobacco dependence among smokers who experience varying levels of pain intensity.