Abstract: The fluorinated polyarcylate emulsifier-free emulsion was synthesized by seed emulsion polymerization，using methyl methacrylate (MMA)，butyl acrylate (BA) and hexafluorobutyl methacrylate (HFMA) as monomers. The influences of the content of polymerizable emulsifier ammonium allyloxtmethylate nonylphenol ethoxylates sulfate (DNS-86) and the fluorine-containing monomer (HFMA) on the properties of electrolyte stability of the emulsifier-free emulsion and water resistance of film formed were discussed. The formed films were characterized by Fourier transform infrared spectrum，differential scanning calorimetry and thermogravimetry analysis. The results showed that both the electrolyte stability of the emulsifer-free emulsion and the water resistance of the film formed were improved comparing with the traditional emulsion polymerization one，and that both the film hydrophobic and thermal stability were clearly improved due to the fluorine-containing monomer effectively involved in the polymerization.