Abstract: Fluorine containing polyacrylate with fluorine-rich surfaces was synthesized with efficient crosslinking agent such as 4-hydroxybutyl acrylate (4HBA), butyl acrylate (BA), dodecafluoroheptyl methacrylate (G04), using a technic of core-shell polymerization in which fluoride monomer was dropped at last. Infrared spectrometer, thermo gravimetric analyzer, differential scanning calorimetry, atomic force microscope, X-ray photoelectron spectrometer and contact angle analyzer were used to characterize properties of the emulsion. Results showed that the contact angle of polymer dry film to water and oil was 94° and 81°, respectively. The surface energy was 31 J/m2 when the mass content of G04 was 20% of the total polymerization monomers. The optimal mass fraction of 4HBA was 4%. And fluorine tended to enrich in the surface during film formation.