Fluorinated polyurethane (PUFPA) emulsions of different fluorine monomers were synthesized by isophorone diisocyanate (IPDI), polyether diol (MDEA), N-mthyldiethanolamine (MDEA), trimethylolpropane (TMP), and Perfluoroalkyl acrylate (FA) via miniemulsion polymerization. The effects of the amount of FA on the properties of the self-organized gradient structure of latex film were investigated by infrared spectroscopy, surface free energy, atomic force microscope, scanning electron microscopy and X-ray photoelectron spectroscopy. The results shows: with the increasing of the amount of FA; the surface free energy difference between the F-A (film-air) surface and the F-P (film-polytetrafluoroethylene substrate) surface of PUFPA40 % film is obvious, the cross-section of PUFPA40% film is stratifie, the fluorinated component (FPA) is enrich at F-A surface and gradient structure is more obvious when the amount of FA is 40 %; The surface contact angle (water) of the latex film F-A reached 132.5?, which increased hydrophobicity significantly, and the gradient structure of PUFPA is more obvious after being heat treatmented (110 ℃/2 h).