Abstract In this study, poly(acrylic)/SiO 2–TiO 2 core–shell nanoparticle hybrid thin films were successfully synthesized by microwave-assisted polymerization. The coupling agent 3-(trimethoxysilyl) propyl methacrylate (MSMA) was hydrolyzed with colloidal SiO 2–TiO 2 core–shell nanoparticles, and then polymerized with two acrylic monomers and initiator to form a precursor solution. The results of this study showed that the spin-coated hybrid films had relatively good surface planarity, high thermal stability, a tunable refractive index (1.525 < n < 1.870), and excellent optical transparency, in the visible range. The prepared hybrid thin films were applied to develop a three layer antireflective (AR) coating on the microscope slide glass (FEA glass) substrate. Results showed that the reflectance of the AR coating on the FEA glass was less than 0.5% in the visible range, which was lower than that of an FEA glass substrate. Our study demonstrated an alternative approach to the preparation of high refractive index poly(acrylic)/SiO 2–TiO 2 core–shell nanoparticle hybrid thin films, for potential use in optical applications.