Despite the large body of research on the risk factors for posttraumatic stress disorder (PTSD), few studies have examined specific personality factors that may be associated with risk for PTSD or the potential mechanisms that may underlie the association between personality and PTSD. Thus, this study sought to examine the relation between the behavioral inhibition system (BIS), a motivational brain-based system associated with the experience of anxiety, and probable posttraumatic stress disorder (PTSD) status. Further, we examined the mediating role of experiential avoidance in the relation between BIS sensitivity and PTSD. Participants included 291 undergraduates who indicated they had experienced a potentially traumatic event at some point in their life. As expected, significant associations were found between BIS sensitivity, experiential avoidance, and probable PTSD status. Results indicated that BIS scores significantly predicted probable PTSD status above and beyond other relevant covariates, including anxiety symptom severity. Further, this association was found to be fully mediated by experiential avoidance.