CeO₂/polymer nanoparticles have drawn considerable attention for their excellent UV absorption properties. However, many challenges still exist in the successful incorporation of ceria into the polymer matrix for the easy agglomeration and photocatalytic activity of CeO₂ nanoparticles. Herein, we address these issues by constructing three-layer structured nanoparticles (M-CeO₂@SiO₂) and incorporating them into a polymer matrix through a mini-emulsion polymerization process. During this process, small-sized nano-ceria became uniformly anchored on the surfaces of monodisperse silica particles first, and then the particles were coated with an MPS/SiO₂ shield. The morphology and dispersion of the nanoparticles were investigated using scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The performance of the hybrid films was characterized using UV-vis absorption spectroscopy (UV-vis) and water contact angle (WCA) measurements. Results showed that the M-CeO₂@SiO₂ nanoparticles exhibited a three-layer structure with a mean diameter of 360 nm, and they possess good compatibility with acrylic monomers. After the addition of M-CeO₂@SiO₂, hybrid films exhibited enhanced UV absorption capacity as expected, accompanied by an obvious improvement in hydrophobicity (the water contact angle increased from 84.2° to 98.2°). The results showed that the hybrid films containing M-CeO₂@SiO₂ particles possess better global performance as compared with those containing no particles.