For a long time, a large number of sandstone cultural relics have been exposed to the outdoors, and they are facing unprecedented threats. Curing perhydropolysilazane at varied pyrolysis times results in a series of SiON solids. Fourier transform infrared absorption spectroscopy (FTIR) results show that the Si−H bond disappears at 2163 cm−1, and that the Si−O peaks at 460 cm−1, becoming stronger during the pyrolysis of Perhydropolysilazane (PHPS) to SiON solids. X-ray photoelectron spectroscopy (XPS) results indicate a decrease in the proportion of N atoms from 22.71% to 3.38% and an increase in the proportion of O atoms from 59.74% to 69.1%, indicating a gradual production of SiO2 from perhydropolysilazane. To protect the sandstone, the SiON protective layer and the commonly used protective materials—acrylic resin and polydimethylsiloxane—are applied. When compared to sandstone treated with acrylic resin B72 and polydimethylsiloxane coatings, SiON-coated sandstone effectively reduces porosity and water absorption. Ageing tests have shown that the SiON-coated sandstone is effective in resisting crystalline damage from sodium sulfate. These thenardites can change shape during formation, allowing their widespread distribution in different locations in the sandstone. The surface thenardite of the SiON-treated samples was smaller than that of the polydimethylsiloxane and acrylic resin B72-treated samples, while the untreated samples were flaky with obvious dehydration characteristics.