This study examined the potential role of catastrophic cognitions in mediating threat expectancy during fear conditioning and extinction in Posttraumatic Stress Disorder (PTSD). It was hypothesised that participants with PTSD would display heightened catastrophic thinking and greater threat expectancy during fear extinction; the potential for catastrophic cognitions to mediate the relationship between PTSD symptom severity and threat expectancy during fear extinction was also assessed. Fifty-nine participants (21 PTSD, 19 TEC, and 19 NTEC) completed measures of catastrophic thinking (CCQ-M and PTSI) and the differential fear conditioning and extinction paradigm. The PTSD group demonstrated significantly greater trauma-specific catastrophic thinking than both control groups, but group differences in more generalised catastrophic cognition were non-significant. The PTSD group also exhibited more rapid fear acquisition and impaired fear extinction. Trauma-related catastrophic thinking did not mediate the relationship between PTSD symptoms and threat expectancy in the early extinction phase of the fear conditioning paradigm.