Optical nanocomposites based on transparent polymers and nanosized pigment particles have usually been produced at low particle concentrations due to the undesirable optical scattering of the pigment particles. However, the contribution of the particles to many physical properties is realized at high concentrations. In this study, nanocomposites were prepared with transparent polystyrene (PS) and organophilic CeO2 nanoparticles using various compositions in which the particle content was up to 95 wt%. The particles, capped by 3-methacryloxypropyltrimethoxysilane (MPS), were dispersed into PS and the transmittance of the spin-coated composite films was examined over the UV-visible region. When the particle concentration was <20 wt%, the transmittance of the films showed a first-order exponential decay as the Rayleigh scattering theory proposes. However, a positive deviation was observed from the decay function for higher particle contents. The improvement in transmittance may be a consequence of interference in the multiple scattering of light by the quasi-ordered internal microstructure that gradually develops as the particle concentration increases.