A protective sol (IBIES-TiO2@SiO2 composite sol) was synthesized by sol-gel method with isobutyltriethoxysilane (IBTES), ethyl orthosilicate and butyltitanate as the main components. In this study, a super-hydrophobic self-cleaning coating was prepared in one step by using spray method. The phase composition and micro morphology of IBTES-TiO2@SiO2 and the super-hydrophobicity, self-cleaning and weather resistance of the coating surface after sandstone protection were studied through XRD, FT-IR, SEM, TEM and other measurements. The results show that IBTES-TiO2@SiO2 composite coating has a water contact angle of up to 162°, and has excellent self-cleaning property. After spraying treatment, the water vapor transmission rate of sandstone only reduces by 3.4%. Obviously, the water vapor transmission performance is excellent. When the addition amount of TiO2@SiO2 is 0.7% (mass fraction), it meets the super-hydrophobic performance of sandstone cultural relics while taking into the water vapor permeability. IBTES-TiO2@SiO2 composite coating also has excellent weather resistance. The addition of TiO2@SiO2 particles effectively improves the acid resistance, alkali resistance and ultraviolet aging resistance of sandstone. In 300 h artificial accelerated aging experiment, the surface coating of sandstone still has super-hydrophobic protection properties. IBTES-TiO2@SiO2 composite coating has a good protective effect on sandstone cultural relics. Hence, IBTES-TiO2@SiO2 composite coating is highly promising for the protection of sandstone cultural relics.