The invention relates to a composite microsphere with a radial fibrous mesoporous shell layer/hollow nuclear layer structure and a preparation method of the composite microsphere. The composite microsphere is provided with a cavity, a nuclear layer and a mesoporous shell layer, wherein the mesoporous shell layer is provided with radial fibrous mesoporous channels. The composite microsphere is highin sphericity and surface regularity, uniform in particle size distribution and high in monodispersity and strength. The preparation method of the composite microsphere is simple and feasible and facilitates industrialization; preparation of the radial fibrous mesoporous shell layer and removal of an organic template can be completed by means of a one-step method. The composite microsphere has the advantages of high light scattering efficiency, large specific surface area, low density, high porosity and the like, can be widely applied in light diffusion materials and used as a light diffusionagent for heavy haze and can also be adopted in the fields of fillers of coatings, cosmetics, catalysts and water treatment.