The invention provides titanium dioxide composite filler, a preparation method thereof and a reflective heat insulation coating, and belongs to the technical field of coatings. According to the invention, activation and modification are carried out on hollow glass microspheres, so that activity of surfaces of the hollow glass microspheres is effectively improved, compact deposition of titanium dioxide crystals on the surfaces of the microspheres is ensured, and the titanium dioxide film coating rate and coating uniformity on the surfaces of the glass microspheres are improved. The concentration of a titanium tetrachloride ethanol solution is controlled, and the addition speed and stirring speed of the titanium tetrachloride ethanol solution are controlled, so that titanium dioxide crystalswith different particle diameters are formed, and emissivity of the coated microspheres to sunlight is greatly improved. Reflective heat insulation performance of the reflective heat insulation coating prepared by the titanium dioxide composite filler is remarkably improved, hemispherical emissivity, sunlight reflection ratio and near-infrared emissivity all exceed 90%, and excellent comprehensive performance such as adhesive force, flexibility, acid resistance, alkali resistance and the like are achieved.