Hollow silica spheres (HSS) with the controllable diameters of 1.0 to 5.0 μm were successfully synthesized by adjusting the initial doubly distilled water volume in mixed ethanol–water solvent based on a complex approach that dispersion polymerization coexisted with a sol–gel process. The size of the HSS was uniform and the surface of the shell was smooth as observed by SEM. The FT-IR spectrum indicated that the inside core was completely removed. The thermal property and the compositions of core–shell spheres were investigated by TG-DSC.