PAES/SiO2 hybrid emulsion with inorganic silica cover organic latexes structure was prepared by dropping TEOS to the SiOH surface functionalized polyacrylate (PAES), which was synthesized by addition of KH570 to acrylic polymer emulsion in the addition of monomers up to 70% during the emulsion polymerization. Transmission electron microscopy (TEM) photos indicate that acrylic latexes were covered by inorganic silica components. Fourier transform infrared (FTIR) confirms that KH570 was copolymerized with acrylate monomers and Si-O-Si crosslinking bonds were found when addition of TEOS to PAES. The effects of KH570 and TEOS concentration on the properties of hybrid emulsions and films were investigated, the results indicates that the particle diameters of PAES emulsion increase with the increasing of KH570 concentration, the water-/ethanol- resistance, and gloss of PAES films display excellent properties when the concentration of KH570 is 3 wt%. The particle diameters of PAES/SiO2 hybrid emulsion slightly increase with the increase of TEOS concentration. The water-/ethanol-resistance, hardness and gloss of hybrid films exhibit better properties as the amount of TEOS is 30 wt%. The hybrid films composed of the continuous polyacrylate components, polysiloxane oligomers and Si-O-Si crosslinking polymers. Thermogravimetric analysis (TGA) curves demonstrate that hybrid films display good thermal stability than the PAE and PAES films.