The invention belongs to the field of preparation of composite titanium dioxide, and relates to a preparation method of composite titanium dioxide. The preparation method comprises the following steps: mixing and stirring oxalic acid, absolute ethyl alcohol and deionized water to obtain a stirred solution; mixing tetrabutyl titanate and absolute ethyl alcohol to obtain a mixed solution; adding themixed solution in the stirred solution, standing, placing precipitates in a water bath for evaporation, and drying to obtain a dried material; adding hydrochloric acid, mixing, standing, and filtering to obtain a filter residue, placing the filter residue in hot water, stirring, filtering to obtain a filter residue a, grinding, sieving to obtain a sieved material, adding a coupling agent and an ethanol solution, mixing, oscillating, performing suction filtering, drying, grinding to obtain a ground material, adding absolute ethyl alcohol and deionized water, mixing, stirring, adding a flourescent brightener, centrifuging, and performing vacuum drying on precipitates to obtain a dried material a; and mixing modified calcium carbonate, a dispersant, sodium dodecyl benzene sulfonate and water, grinding, adding the dried material a, grinding, dehydrating, drying, and crushing to obtain the composite titanium dioxide.