Cationic fluorinated acrylate polymer emulsion was prepared by emulsion polymerization of styrene (St), Methacrylatoethyl trimethyl ammonium chloride (DMC), butyl acrylate (BA), 2-hydroxyethyl acrylate (HEA), Perfluoroalkylethyl methacrylate (FM) using poly(vinyl alcohol) (PVA) as emulsifier and using Fe2+-H2O2 as initiator. FT-IR, 1H-NMR, TEM, DSC and contact angle measurements characterized the polymer structure, particle size and morphology of the emulsion, surface property of the film, respectively. The results show that the emulsion presents monodisperse and particles size is 90-100nm. The surface free energies of the copolymer films decrease with increasing the concentration of FM. Annealing treatment enhanced the enriching tendency of fluorine-containing group at copolymer-air interface and decreased the surface free energies.