This cross-sectional study aims to explore the exposure to sexual harassment and assaults, coping, and posttraumatic stress disorder (PTSD) and their associations among Australian ambulance personnel. The study was conducted on 492 stratified and randomly selected ambulance personnel across three Australian states in 2017. A telephone interview administered questionnaire was used to collect data on exposure to sexual harassment and assault (Life Event Checklist for the Diagnostic and Statistical Manual of Mental Disorders, Fifth Edition (DSM-5)), coping (Brief Coping Orientations to Problems Experienced (Brief COPE)), and PTSD (PTSD checklist for DSM-5). Descriptive and bivariate statistics were used for data analysis. The study found that female ambulance personnel were more likely to be exposed to sexual harassment and assault directly and to sexual harassment as part of their jobs than their male colleagues. Female staff were more likely to use religious, emotional and instrumental support, and self-blame as their coping strategies. Frequent exposure to sexual harassment was significantly associated with an increased risk of PTSD. Greater use of maladaptive coping strategies was significantly associated with an increased risk of PTSD. Greater use of adaptive coping strategies was not significantly associated with a reduced risk of PTSD. Findings from this study suggest that strategies to manage frequent exposures to sexual harassment and its impacts, especially for female ambulance personnel, should be implemented to reduce the risk of PTSD. Further investigation into the effective use of adaptive coping strategies may provide explanations for the insignificant associations between a greater use of adaptive coping strategies and PTSD.