A novel polymer/SiO2 hybrid emulsion (PAES) was prepared by directly mixing colloidal silica with polyacrylate emulsion (PAE) modified by a saline coupling agent The sol-gel-derived thin films were obtained by addition of co-solvents into the PAES. The effects of gamma-methacryloxypropyltrimethoxysilane (KH-570) content and co-solvent on the properties of PAES films were investigated Dynamic laser scattering (DLS) data indicate that the average diameter of PAES (96 nm) is slightly larger than that of PAE (89 nm) Transmission electron microscopy (TEM) photo discloses that colloidal silica particles are dispersed uniformly around polyacrylate particles and some of the colloidal silica particles are adsorbed on the surface of PAE particles The crosslinking degree data and Fourier transform infrared (FT-IR) spectra confirm that the chemical structure of the PAES is changed to form Si-O-Si-polymer crosslinking networks during the film formation Atomic force microscope (AIM) photos show the solvent induced sol-gel process of colloidal silica and the Si-based polymer distribution on the film surface of the dried PAES Thermogravimetric analysis (TGA) curves demonstrate that the PAES films display much better thermal stability than PAE.