AbstractCoal spontaneous combustion (CSC) has hindered the utilization of coal resources and the development of the global economy for centuries. At present, many materials are used for preventing and extinguishing CSC fires, and different types of materials have various sites of action. In this paper, research on CSC fire prevention and extinguishing materials is reviewed and proposed. The preparation schemes and effects of physical barrier materials, chemical inhibitors, composite materials, and other fields of fire prevention materials were discussed. The improved compounding schemes of CSC inhibiting materials were analyzed regarding the characteristics of base materials and material properties. It was found that in the field of fire prevention materials, plant extracts, hydrolyzed proteins, biomass, and other green recycling materials have gradually become the new trend in materials. The composite material has a synergistic physical barrier and chemical inhibition and has a good inhibitory effect on coal heat storage and group activation, which has become an inhibitory material that is highly concerning. CSC inhibiting technology involving microbial control has emerged and exhibits notable characteristics, including a green cycle and long action time, but its application still needs to control the coexistence of heterogeneous microorganisms and improve the environmental livability. High‐quality firefighting materials, which are used in preventing battery fires, fighting building fires, inert coatings of cotton fabric, and other fields, have potential applicational value for CSC prevention. This review aims to provide new ideas for the research of CSC fireproof materials.