Abstract: Foam fire prevention and extinguishing technology is one of the effective means for the prevention and control of coal spontaneous combustion in goafs. To improve foam stability and enhance its efficacy in inhibiting coal spontaneous combustion, curcumin (Cur)-loaded montmorillonite (MMT) foam-stabilizing particles (Cur-MMT) are prepared by the solution blending method, with hydrocarbon surfactants, the polyphenolic antioxidant curcumin (Cur), inorganic particulate montmorillonite (MMT), and biomass gel as the main raw materials. Cur-MMT composite gel foam is further developed, and the influence characteristics of Cur-MMT composite gel foam on the low-temperature oxidation performance and microstructure of coal are analyzed. The results show that the liquid drainage rate of Cur-MMT composite gel foam is 11.53% within 120 h, indicating that the foam structure can be maintained stably. The yield strain corresponding to the intersection of storage modulus (G') and loss modulus (G'') of Cur-MMT composite gel foam is increased by 12.5% compared with that of conventional gel foam, indicating that the shear deformation resistance of the gel foam is enhanced by Cur-MMT, and a more stable network structure is formed. The contact angle of the foam on the coal surface is decreased by 56.53% compared with that of pure aqueous solution; thus, the coal surface can be effectively wetted, and the surface free energy of the coal sample is increased by 10.06%. The comprehensive characteristics of microstructural changes show that the surface fractal dimension D_F1 and spatial fractal dimension D_F2 of foam-treated coal samples are lower than those of raw coal, and the pore surface roughness and pore spatial complexity are reduced. Meanwhile, the diffraction peak intensity of calcite for treated coal samples is increased, the average stacking height L_c is decreased by 10.68%, and the stacking number of aromatic lamellae M_c is decreased by 10.81%. In the performance evaluation, an inhibition rate of 75.20% on coal mass is achieved by Cur-MMT composite gel foam, which is 30.58% higher than that of conventional gel foam. The activation energy of coal samples in the combustion stage is increased by 19.58%, and the peak areas of methyl and methylene functional groups in coal are decreased; thus, the development process of coal spontaneous combustion is delayed. In the mechanism analysis, a dense foam film is formed at the gas-liquid interface by Cur-MMT foam-stabilizing particles and biomass gel, by which effective wetting and adhesion on the coal mass surface are achieved. Meanwhile, a colloidal film is formed on the coal mass surface through gelation, by which the contact between the coal mass and oxygen is blocked, and the oxidation reaction of the coal mass is inhibited. New insights are provided by the research results for the exploration of novel gel foam fire prevention and extinguishing materials and their synergistic foam-stabilizing and inhibition effects.