In the presence of 3-aminopropyltriethoxysilane (APTES), the transparent and yellowish poly(methyl acrylate-co-itaconic anhydride)/TiO2 [P(MA-co-Itn)/TiO2] hybrid materials were prepared from the copolymer of methyl acrylate and itaconic anhydride [P(MA-co-Itn)] and tetrabutyl titanate (TBT) via a sol-gel process. At first, the triethoxysilane groups were incorporated into the copolymer P(MA-co-Itn) as pendant side chains by the aminolytic reaction between the itaconic anhydride units of the copolymer and the amino group of 3-aminopropyltriethoxysilane (APTES), and then the covalent bonds between the organic and inorganic phases were introduced by the hydrolysis and polycondensation of the triethoxysilane groups on the copolymer with TBT. FTIR analysis proved the existence of the covalent bonds. The influences of APTES on glass transition and morphology of the hybrid materials was studied by differential scanning calorimetry, scanning electron microscope, and atomic force microscope.