Abstract: In view of problems of poor fluidity, unsatisfactory fire-extinguishing effect and high cost of existing mine-used anti-fire extinguishing resistant material,inorganic clay composite superabsorbent resin was synthesized by aqueous solution polymerization method, and its structural characterization and thermal stability were measured. The resistive properties were studied combined with heating process of coal spontaneous combustion. The results of infrared spectrum and thermal stability analysis show that the prepared composite superabsorbent resin has main functional group with high water absorption characteristics and high thermal stability. The coal samples were treated with CaCl2, ascorbic acid and composite superabsorbent resin to resist the oxidation, and the oxidation kinetics and index gas tests were carried out on the coal samples after the inhibition. The results show that compared with the raw coal, CaCl2 and ascorbic acid resistant coal sample, composite superabsorbent resin resistant coal sample has the smallest oxygen consumption when the temperature of coal sample reaches 70 °C, and its intersection temperature is the highest, the initial temperature required to produce CO and CO2 is higher, which indicates that the composite superabsorbent resin has better inhibition effect on coal spontaneous combustion.