Work-related suicide exposure may significantly contribute to the risk of burnout in first responders. This study assessed the exposure to suicide, burnout, and coping mechanisms in emergency medical services in Poland, including psychosocial determinants, such as age, gender, and access to psychological support. The level of burnout was assessed using the Link Burnout Questionnaire (LBQ), and coping was measured using the Coping Inventory for Stressful Situations (CISS). Data were analysed using a series of variance analyses and a partial least squares structural equation modelling. The study showed that 98% of emergency medical services personnel reported work-related suicide exposure. The LBQ score indicated symptoms of burnout, in particular relational deterioration, and the CISS showed low levels of emotion-oriented coping. Physicians reported higher levels of psycho-physical exhaustion than paramedics and nurses. Access to psychological support in the workplace was related to lower levels of burnout. Emergency medical services personnel are frequently exposed to suicide, which may be related to the risk of occupational burnout, and coping strategies used in this occupational group are often not optimal. Preventive measures, such as training emergency medical services personnel in regard to effective coping strategies, are needed, and personnel should be encouraged to access mental health services and supports.