The polyacrylate/silica composite latexes were prepared by directly mixing silica particles with polyacrylate modified by γ-methacryloxypropyltrimethoxysilane (MPS). Fourier transform infrared (FTIR) spectra and X-ray photoelectron spectroscopy (XPS) analysis of polyacrylate/silica composite films confirmed the sol-gel processes occurred to form Si–O–Si crosslinking bonds during the process of film-formation. Transmission electron microscope (TEM) images revealed that the polyacrylate latexes were in contact with silica particles while some silica particles stayed together. Atomic force microscope (AFM) photos showed that organic and inorganic phases were strictly connected with each other and silica particles were embedded in the polymeric matrix with a size range of 20–50 nm. Differential scanning calorimetry (DSC) curves demonstrated that the composite film with 3% MPS has higher T g than those of pure polyacrylate films.