Homogeneous organic–inorganic hybrid materials with high performance were successfully prepared by mixing (3-methacryloxypropyl) trimethoxysilane (MPMS) capped acrylic resin with titania synthesized by sol-gel approaches. The effects of the titania content, the amount of water and nature of catalysts in the sol-gel as well as the ratios of mixed solvents of butyl acetate and ethanol on the structures and properties of the hybrid materials were studied. Higher titania content, larger amount of water and base catalysis in the sol-gel process, as well as the solvent with higher ratio of butyl acetate to ethanol for the hybrids caused larger size and less open structure of titania phase. The hardness, elastic modulus, thermal stability and refractive index for the hybrid materials improved dramatically with increasing titania content. In general, better prosperities, especially mechanical properties, were achieved for the hybrid prepared under lower water content, pH values (such as acid catalysis) and mB/mE ratio.