Optical transparency and high diffraction efficiency are two essential factors for high performance of the photopolymer. Optical transparency mainly depends on the miscibility between polymer binder and photopolymerized polymer, while diffraction efficiency depends on the refractive index modulation between polymer binder and photopolymerized polymer. For most of organic materials, the large refractive index difference between two polymers accompanies large structural difference that leads to the poor miscibility and thus poor optical quality via light scattering. Therefore, it is difficult to design a high-performance photopolymer satisfying both requirements. In this work, first, we prepared a new phase-stable photopolymer (PMMA) with large refractive index modulation and investigated the optical properties. Our photopolymer is based on modified poly (methyl methacrylate) as a polymer binder, acryl amide as a photopolymerizable monomer, triethanolamine as initiator, and yellow eosin as a photosensitizer at 532 nm. Diffraction efficiency over 85% and optical transmittance over 90% were obtained for the photopolymer. Second, Organic-inorganic nanocomposite films were prepared by dispersing an aromatic methacrylic monomer and a photo- initiator in organic-inorganic hybrid sol-gel matrices. The film properties could be controlled by optimizing the content of an organically modified silica precursor (TSPEG) in the sol-gel matrices. The photopolymer film modified with the organic chain (TSPEG) showed high diffraction efficiency (> 90%) under an optimized condition. High diffraction efficiency could be ascribed to the fast diffusion and efficient polymerization of monomers under interference light to generate refractive index modulation. The TSPEG modified photopolymer film could be successfully used for holographic memory.