In China, 47.3% of state-owned coal mines are located in coal seams that are prone to spontaneous combustion. The spontaneous combustion of coal is the main cause of the generation of a large amount of carbon monoxide, which can cause serious health issues to miners. A new technique using foam-gel formation was developed to effectively control the spontaneous combustion of coal. The gel can capture more than 90% of the water in the grout and at the same time the foam can cover dangerous areas in the goaf by stacking and cooling of foam in all directions. In this study, a mechanism of foam-gel formation was introduced and the optimal proportions of additives were defined based on experiments of different foaming properties, gelling time and water loss rate as the main index parameters. The results of a field application in a coal mine promise that this new technique would effectively prevent coal oxidation in the goaf and reduce the generation of carbon monoxide.