In this study, a simple, convenient and green approach for the preparation of organosiloxane-coated SiO2/CeO2 (SiO2/CeO2/poly(VTMS)) with multilayered hierarchical structure is demonstrated by consecutive surface cerium deposition and organosiloxane grafting on the bare silica spheres. The results of the UV-Vis spectrum and photoluminescence analysis suggest that the fillers may be potentially applied in UV absorbers and bioimaging materials. Moreover, the optical diffusers based on the multilayered spheres can be prepared via a solvent-free UV curing process and exhibit enhanced properties like suitable light transmittance, good diffusion capacity and low-incident angle dependence, which are critical for the optical diffusers. In addition, when the concentration of the fillers was 15 wt%, the optical diffusers presented superior light-diffusing properties among all the as-prepared samples. Thus, the films based on the SiO2/CeO2/poly(VTMS) with multilayered hierarchical structure may open up new possibilities in applications as multifunctional light diffusion films in liquid crystal displays.