Background: Emergency Medical Services personnel (EMSP) are recurrently exposed to chronic and traumatic stressors in their occupation. Effective coping with occupational stressors plays a key role in enabling their health and overall well-being. In this study, we examined the habitual use of coping strategies in EMSP and analyzed associations of coping with the personnel’s health and well-being. Method: A total of N = 106 German Red Cross EMSP participated in a cross-sectional survey involving standardized questionnaires to report habitual use of different coping strategies (using the Brief-COPE), their work-related stress, work-related self-efficacy, job satisfaction, as well as mental and physical stress symptoms. Results: A confirmatory factor analysis corroborated seven coping factors which have been identified in a previous study among Italian emergency workers. Correlation analyses indicated the coping factor “self-criticism” is associated with more work-related stress, lower job satisfaction, and higher depressive, posttraumatic, and physical stress symptoms. Although commonly viewed as adaptive coping, the coping factors “support/venting”, “active coping/planning”, “humor”, “religion”, and “positive reappraisal” were not related to health and well-being in EMSP. Exploratory correlation analyses suggested that only “acceptance” was linked to better well-being and self-efficacy in EMSP. Conclusion: Our results emphasize the need for in-depth investigation of adaptive coping in EMSP to advance occupation-specific prevention measures.