ICD-11 complex post-traumatic stress disorder is a more severe condition than post-traumatic stress disorder, and recent studies indicate it is more prevalent among military samples. In this study, we tested the psychometric properties of the International Trauma Questionnaire, assessed the relative prevalence rates of post-traumatic stress disorder and complex post-traumatic stress disorder in the sample population and explored relationships between complex post-traumatic stress disorder and post-traumatic stress disorder and a range of risk factors. Survey participants (N = 189) were mental health support-seeking former-serving veterans of the Australian Defence Force (ADF) recruited from primary care. Confirmatory factor analysis was used to test the factorial validity of the International Trauma Questionnaire. The latent structure of the International Trauma Questionnaire was best represented by a two-factor second-order model consistent with the ICD-11 model of complex post-traumatic stress disorder. The International Trauma Questionnaire scale scores demonstrated excellent internal reliability. Overall, 9.1% (95% confidence interval = [4.8%, 13.5%]) met diagnostic requirements for post-traumatic stress disorder and an additional 51.4% (95% confidence interval = [44.0%, 58.9%]) met requirements for complex post-traumatic stress disorder. Those meeting diagnostic requirements for complex post-traumatic stress disorder were more likely to have served in the military for 15 years or longer, had a history of more traumatic life events and had the highest levels of depression, anxiety and stress symptoms. The International Trauma Questionnaire can effectively distinguish between post-traumatic stress disorder and complex post-traumatic stress disorder within primary care samples of Australian Defence Force veterans. A significantly greater proportion of Australian Defence Force veterans met criteria for complex post-traumatic stress disorder than post-traumatic stress disorder. Australian military mental health services should adopt the International Trauma Questionnaire to routinely screen for complex post-traumatic stress disorder and develop complex post-traumatic stress disorder specific interventions to promote recovery in Australian Defence Force veterans with complex post-traumatic stress disorder.