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 goal of the current study was 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 a sample of 55 daily cigarette smokers who attempted to quit smoking without using any psychosocial or pharmacological cessation aids. Pain-related anxiety was assessed at baseline using the 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 one-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 four-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 shown to be a significant predictor of early lapse when the sample was limited to smokers who endorsed past four-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.