Safety compliance (SC) and safety participation (SP), which are key factors predicting safety outcomes (e.g., accidents, injuries and near misses), are related but distinct. However, which component is more significant remains controversial. Job burnout is a typical occupational psychological syndrome of employees that impacts safety outcomes, but the role that it plays in the relationship between SC, SP and safety outcomes is ambiguous. To clarify these relationships, Chinese coal mine workers were sampled. Then, hypotheses on the influencing mechanisms were initially proposed and later tested empirically. To conduct this testing, SC and SP scales were revised, and a job burnout scale was developed. The results showed that there were significant relationships between workers’ SC and SP and safety outcomes; meanwhile, exhaustion, cynicism and low professional efficacy had significant effects on these relationships. Job burnout acted as a significant and indispensable moderator. Moreover, workers’ occupational psychological health condition should be considered when improving safety outcomes.