Mine fires have always been one of the disasters that restrict coal mining in China and endanger the life safety of underground workers. The research and development of new fire prevention materials are undoubtedly important to ensure the safe and efficient production of modern mines. At present, the main inhibiting materials used are grout material, inert gas, retarding agent, foam, gel, and so on. In order to explore the current situation of coal spontaneous combustion (CSC) fire prevention, the existing fire prevention materials were reviewed and prospected from three aspects: physical, chemical, and physicochemical inhibition. The results show that, at present, most of the methods of physicochemical inhibition are used to inhibit CSC. Antioxidants have become popular chemical inhibitors in recent years. In terms of physical inhibition, emerging biomass-based green materials, including foams, gels, and gel foams, are used to inhibit CSC. In addition, CSC fire-fighting materials also have shortcomings, including incomplete research on the mechanism of material action, poor stability of inhibitory properties, low efficiency, and economic and environmental protection to be improved. The future research direction of fire-fighting materials will be based on theoretical experiments and numerical simulation to study the mechanism and characteristics of CSC and develop new directional suppression materials with physicochemical synergies. These findings have extremely important implications for improving materials designed to prevent CSC.