Research on polyurethane sponge (PUS), a widely used polymer material, and its flame-retardant performance is of great significance. In this study, PUS was modified to prepare a highly efficient flame-retardant composite using a soaking method. The PUS nearly vanished at 11 s after ignition, and the solid residue rate of the PUS was 5.65 wt% at 750 °C. The net structure, composed of nano SiO₂, was maintained in the modified PUS at 750 °C, and the solid residue rate was 69.23%. The maximum HRR of the PUS decreased from 617 W/g to 40 W/g and the THR of the sample reduced from 33 kJ/g to 9 kJ/g after modification. The results suggested that the modified PUS gained excellent flame-retardant performance. The flame-retardant layer in the modified PUS was amorphous. The surface of the modified PUS was rich in Si, O, and C elements and lacked a N element, suggesting that inorganic flame retardants were abundant on the surface layer of the modified PUS. The Si-O-C vibration and Si-O-Si stretching in the modified PUS indicates that the organic–inorganic hybrid structure formed on the PUS surface, which could be attributed to the polymerization and condensation of the silica precursor. Thus, the modified PUS provided an excellent flame-retardant layer. The results are of interest for producing efficient flame-retardant PUS using a simple method.