Regarding to the problem of low reflection in ultraviolet band of existing white thermal control coatings, ZnO/SiO2 was used as pigment to prepare a new type of thermal control coating with high reflection in full solar spectrum. With zinc sulphate and sodium silicate as raw materials, ZnO/SiO2 composite powder was synthesized via the combined method of chemosynthesis and high-heat treatment. The crystal morphology and microstructure of ZnO/SiO2 composite powder were observed by XRD, SEM and TEM, and the optical performance of ZnO/SiO2 was characterized by UV/Vis spectrophotometer. The thermal control coating was prepared with ZnO/SiO2 composite powder as pigment and potassium metasilicate as adhesive. By analyzing the optical performance of various pigment-to-adhesive ratios and thicknesses, the best coating formula which has the minimum solar absorptance was confirmed. The results showed that ultraviolet absorptance of ZnO/SiO2 composite powder was 0.09, and the reflection in ultraviolet band of ZnO/SiO2 was above 88% which was much higher than traditional ZnO pigment, proved better optical properties. The mainly mechanism of the higher reflection is the refractive index of ZnO and SiO2 was quite different so that the reflection and refraction produced at the interface between them were stronger, according to this principle, ZnO/SiO2 overcome the problem of lower ultraviolet reflectance. After optimized experiments, preparation method of the thermal control coating was obtained:pigment-to-adhesive ratio is 2:1 and the thickness of the coating is 100~140 μm. The solar absorptance and infrared emittance of optimized ZnO/SiO2 thermal control coating was 0.12 and 0.92, respectively. Comparing to traditional ZnO thermal control coatings, the ZnO/SiO2 thermal control coating performs better in reflection of ultraviolet band, and at the same time, equipped with high reflection in full solar spectrum. In conclusion, the ZnO/SiO2 thermal control coating has a good application prospect in the new generation of spacecraft as it can satisfy the needs of high efficiency and long service life.