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Research within physical education has begun to focus on psychological outcomes of teachers’ perceptions of their work environments, and mediating variables that support adaptive coping processes. This study examined the relationships between role stress, emotional intelligence, emotional exhaustion, and affective commitment among secondary physical educators (N = 246). Survey results were analyzed through factor analysis and structural modeling. Role ambiguity positively influenced emotional intelligence. Emotional intelligence positively influence emotional exhaustion and affective commitment. Role ambiguity influenced emotional exhaustion directly and indirectly through emotional intelligence. Role conflict directly influenced emotional exhaustion and affective commitment, and role overload directly influenced affective commitment. Enhancing emotional intelligence may promote adaptive emotional responses. Reducing perceptions of role stress may be an important antecedent.