Coal mine accidents seriously affect people’s safety and social development, and intelligent mines have improved the production safety environment. However, safety management and miners’ work in intelligent mines face new changes and higher requirements, and the safety situation remains challenging. Therefore, exploring the key influencing factors of miners’ unsafe behaviors in intelligent mines is important. Our work focuses on (1) investigating the relationship and hierarchy of 20 factors, (2) using fuzzy theory to improve the decision-making trial and evaluation laboratory (DEMATEL) method and introducing the maximum mean de-entropy (MMDE) method to determine the unique threshold scientifically, and (3) developing a novel multi-criteria decision-making (MCDM) model to provide theoretical basis and methods for managers. The main conclusions are as follows: (1) the influence degree of government regulation, leadership attention, safety input level, safety system standardization, and dynamic supervision intensity exert the most significant influence on the others; (2) the causality of government regulation, which is the deep factor, is the highest, and self-efficacy displays the smallest causality, and it is the most sensitive compared to various other factors; (3) knowledge accumulation ability, man–machine compatibility, emergency management capability, and organizational safety culture has the highest centrality among the individual factors, device factors, management factors, and environmental factors, respectively. Thus, corresponding management measures are proposed to improve coal mine safety and miners’ occupational health.