Purpose: Understanding how veterans appraise their post-deployment experiences could provide insight into better assisting their deployment transitions. We aimed to assess the factor structure of positive and negative post-deployment appraisals in Australian veterans and to examine the resultant factors in their relationship with military stress and psychological health. Method: Questions capturing post-deployment attitudes were developed by the researchers in collaboration with veterans. The questions were administered to 1938 veterans and the results factor analysed. The relationships between post-deployment appraisal, military stress and psychological health were examined using Structural Equation Modelling. Results: A three-factor solution was found for the post-deployment appraisal questions; representing personal development, lack of recognition, and appreciation of life and country. Military stress was associated with the three factors and psychological health. The three factors were weakly to moderately associated with psychological health. Mediation between military stress and psychological health by any post-deployment appraisal factor was minimal. Conclusions: Post-deployment appraisal measures three important attitudes and concerns of veterans after deployment. Military stress is associated with the post-deployment appraisal factors. However, the factors did not mediate the relationship between military stress and psychological health. These factors provide insight into how veterans appraise their complex array of post-deployment experiences, and may provide useful in regard to transitions and integration into civilian life.