Gas leakage seriously threatens the safety of workers in coal mines. Spraying the gas-sealing coating is one of the effective methods to relieve gas leakage. However, the hydrophobic property of coal makes it difficult for the gas-sealing coating to penetrate the coal. The effect of surfactants on the properties of the hybrid organic-inorganic, gas-sealing coating was systematically studied. Analysis of the influence of different surfactants on the contact angle of coating and coal shows that the contact angle reduction of tributyl phosphate (TBP) is unaffected by the emulsion concentration. The reduction is more than 30%, which effectively improves the wettability of the coal surface. Further, TBP addition can optimize the micro-morphology, internal microstructure, and bonding strength. TBP addition can also facilitate a close contact on the interface, thus achieving effective penetration within the coal sample and enhancing the gas-sealing performance of the coating. In addition, this study explores preliminarily the curing mechanism and synthetic model of the coating, providing a new theoretical basis for the development of gas-sealing coatings.