Coal fires, most of which are triggered by the spontaneous combustion of coal, cause a huge waste of resources and release poisonous and harmful substances into the environment, seriously threatening the safety of industrial production. Gel flame retardant plays a core role in coal fire prevention and extinguishing. Most gel flame retardants used in coal fires possess good sealing and oxygen isolation properties, but it is difficult for them to flow deep into fire areas due to their low fluidity. Some fire extinguishing agents with good fluidity lack leak-blocking performance. In order to simultaneously improve the fluidity, leakage sealing, and oxygen isolation effects of coal fire extinguishing colloids, a novel, pH-sensitive, sol-gel transition colloid was prepared using low methoxyl pectin (LMP), calcium bentonite (Ca-Bt), sodium bentonite (Na-Bt), and water as the main components. When the initial sol-state colloid absorbed acid gas products from coal combustion, the pH value decreased and a large amount of Ca2+ in Ca-Bt precipitated, thus immediately growing calcium bridges with LMP molecules that formed a three-dimensional network structure for gelation. The optimum ratio of the new colloid was determined through X-ray diffraction, tube inversion, shock shear-temperature scanning, and genetic algorithm. By testing the fire extinguishing performance of the colloid, the findings proved that the product had good oxygen isolation performance, strong adhesion ability, high thermal stability, and strong inhibition effects on coal combustion.