The spontaneous combustion and gas explosion induced by crushed small coal pillars and the residual coal of adjacent goaf will cause a large amount of coal loss and casualties of workers. Moreover, it also seriously pollutes the environment and aggravates the greenhouse effect. To effectively block small coal pillars and fracture zones of adjacent old workings is the key to prevent gas and coal spontaneous combustion in small coal pillars. However, the commonly used blocking materials at present are easy to shrink and chap after air drying, and they have no chemical inhibitory property. Thus, these materials cannot realize the coordinated prevention of gas and coal spontaneous combustion. In this paper, a low-cost and eco-friendly Synergistic Inhibiting and Sealing Material (SISM)with strong inhibitory properties is proposed. The optimal ratio of the material was determined by experiments. The inhibitory properties of the material are analyzed by testing and comparing the generation rate of free radical and CO generation rate. The experimental results showed that the optimal molar ratio of main antioxidant and auxiliary antioxidant was 5:2, and the optimal mass ratio of synergistic antioxidant and high water material was 1:8. Secondly, SISM can prevent or delay the production of new free radicals during coal spontaneous combustion, significantly reduce the concentration of free radicals in coal and finally delay the process of coal spontaneous combustion. Thirdly, both physical and chemical inhibitory properties are taken into account when preparing SISM. Hence, it can maintain both high inhibitory properties in the whole temperature range and the inhibition effect on coal-oxygen compound reaction, which is significantly better than MgCl2 and yellow mud (YM) with only physical inhibition.