The present investigation examined whether daily smokers with posttraumatic stress disorder (PTSD), as compared to daily smokers with either anxiety psychopathology or no current Axis I psychopathology, have decreased success in the early phases of a self-guided smoking quit attempt. Participants were 140 daily smokers (81 women; M (age) = 29.5; SD = 11.9; range = 18-65 years); approximately one-third of the sample met criteria for current PTSD (n = 47), one-third met criteria for other current anxiety disorders (without PTSD; n = 33), and one-third did not meet criteria for any current Axis I disorder (n = 60). Consistent with prediction, membership in the PTSD group, compared to membership in the other anxiety disorders group and the group with no current Axis I psychopathology, was associated with increased risk of lapse during the first week following quit day. Additionally, daily smokers with PTSD and other anxiety disorders were at significantly increased risk of relapse during the first week post-cessation compared to persons without Axis I psychopathology. However, the PTSD group and the other anxiety disorders group did not differ from one another in terms of relapse. Results suggest that PTSD is associated with increased risk of smoking lapse and relapse compared to smokers with no current Axis I psychiatric problems, and increased risk of early smoking lapse but not relapse, as compared to those with other anxiety disorders. Findings provide novel evidence that PTSD, and perhaps anxiety disorders more generally, may be important factors in reducing the odds of successful unaided quit attempts in the early phases of cessation.