A novel fire-preventing composite gel, mainly made from steel slag (SS) and silica fume (SF), was created for a coal mine’s spontaneous combustion. The gelation mechanism of the steel slag-based composite gel (SSG) was investigated using X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), and field emission scanning electron microscopy (SEM). The findings suggest that SSG is generated through the processes of hydration and geopolymerization involving SS and SF. And in the alkaline milieu of a 1.5 M water glass solution, SSG manifests enhanced strength and water retention capacities. Moreover, the fire prevention and extinguishing performance of the SSG was analyzed and verified using low-temperature oxidation, thermogravimetry, and low temperature nitrogen adsorption experiment (LTNA). The SSG has proven highly effective in suppressing spontaneous coal combustion by inhibiting CO production, raising the coal oxidation temperature, and reducing the contact area between oxygen and the coal body.