With the development of science and technology and the increasing importance attached by to these domains by the state and government departments in recent years, China’s coal production and safety supervision level continue to increase. However, the prevalence of frequent coal mine safety accidents has not been effectively curbed. The main purpose of this study was to explore the mediating role of work engagement in the relationship between psychological capital and safety citizenship behavior among Chinese coal miners. Data for 317 coal miners were collected from five coal and energy enterprises. The Psychological Capital Questionnaire (PCQ), the Job Engagement Scale (JES), and the Safety Citizenship Behavior Scale (SCBS) were used to evaluate the coal miners’ psychological capital, work engagement, and safety citizenship behavior. The causal steps approach and bootstrap Method were used in this study to assess the proposed mediation models. A correlation analysis indicated that psychological capital, work engagement, and safety citizenship behavior were significantly correlated with each other. Furthermore, the mediation analysis showed that work engagement mediated the relationship between psychological capital and safety citizenship behavior. Psychological capital does not only have a direct impact on coal miners’ safety citizenship behavior, but it also has an indirect impact on coal miners’ safety citizenship behavior via work engagement. Therefore, effectively enhancing an individual’s psychological capital and work engagement may be a basic factor determining coal miners’ safety citizenship behavior, which further promotes safety production within the enterprise.