This study successfully improved the optical properties of silica/UV-cured polymer composite films made of hollow silica nanoparticles having a hierarchical structure. The particles were synthesized by an inorganic particle method, which involves two steps of sol-gel silica coating around the template and acid dissolution removal of the template. The pH of the acid was varied to achieve different hierarchical structures of the particles. The morphologies and surface properties of the obtained particles were characterized before dispersing in a UV-curable acrylate monomer solution to prepare dispersions for fabricating light diffuser films. The optical properties and the light diffusing ability of the fabricated films were studied. The results revealed that the increased pH of the acid provides the particles with a thinner shell, a larger hollow interior and a higher specific surface area. Moreover, the films with these particles exhibit a better light diffusing ability and a higher diffuse transmittance value when compared to those without particles. Therefore, the composite films can be used as light diffuser films, which is an essential part of optical diffusers in the back-light unit of LCDs. In addition, utilizing the hierarchical particles probably reduces the number of back-light units in the LCDs leading to energy-savings and subsequently lightweight LCDs.