Coal gangue, as an associated product of coal mining, can cause a large number of piles to undergo slow oxidation and spontaneous combustion, resulting in the production of toxic and harmful gases, leading to casualties, environmental damage, and economic losses. Gel foam has been extensively employed as a fire-retardant material in coal mine fire prevention. The thermal stability and rheological properties of the newly developed gel foam were investigated in this study, as well as its oxygen barrier properties and fire extinguishing effect which were evaluated through programmed temperature rise and field fire extinguishing experiments. The experiment indicated that the temperature endurance of the new gel foam was around twice that of the ordinary gel foam, and this resistance decreased with the increment of foaming times. Moreover, the temperature endurance of the new gel foam with a stabilizer concentration of 0.5% was superior to that of 0.7% and 0.3%. Temperature has a negative effect on the rheological properties of the new gel foam, while the foam stabilizer concentration has a positive effect. The oxygen barrier performance experiment results showed that the CO release rate of coal samples treated with the new gel foam rose relatively slowly with temperature, and the CO concentration of coal samples treated with the new gel foam was only 159 ppm at 100 °C, which was significantly lower than 361.1 ppm after two-phase foam treatment and 715 ppm after water treatment. Through simulating the spontaneous combustion experiment of coal gangue, it was demonstrated that the new gel foam has a much better extinguishing effect than water and traditional two-phase foam. The new gel foam cools gradually and does not re-ignite during the fire extinguishing process, while the other two materials re-ignite after being extinguished.