In this study, we provided a designed TiO 2 coating and hydrothermal treatment to synthesize nano-sized TiO 2 /SiO 2 cenospheres (TSCSs) with a rough surface for the application in the solar thermal reflective coating. Various functions of the TSCSs are present, the chemical composition causing significant UVA absorption, hollow interiors have high reflectance of the visible-IR radiation, and strong scattering of incident light. In addition, the low thermal conductivity of TiO 2 , SiO 2 , and the hollow interiors makes the coatings of TSCSs achieve a good thermal insulation. The average infrared reflectance of this coating is 89.61%, and the UVA transmission is only about 22.81%.In addition, the coatings of TSCSs also demonstrate good water resistance on the glass slide due to the closure shell and rough surface to prevent water from entering the pore and cavity.