Abstract：Polyurethane prepolymer (PU) was prepared via the acetone process using isophorone diisocyanate (IPDI), polybutylene adipate (CMA-1044), 1,4-butanediol (BDO) and dimethylolpropionic acid (DMPA) as raw materials. Hyperbranched polyurethane (HBPU) was synthesized through modification of PU by hydroxyl-terminated hyperbranched polymer. Then, novel fluoroalkyl-terminated hyperbranched polyurethane (HBPUF) was prepared by the grafting reaction of perfluorohexyl ethyl alcohol and HBPU. Finally, HBPUF emulsion was obtained by neutralization, adding water, and high-speed stirring operations. Infrared spectrum (IR), proton nuclear magnetic resonance (1H NMR), Transmission electron microscope (TEM), nano particle size, thermogravimetry analyzer (TGA), X-ray photoelectron spectroscopy (XPS) and static contact angle analyzer were utilized to characterize structure of the resultants, particle morphology and average size, thermal stability, chemical compositions as well as hydrophobicity of the latex film. Results showed that fluorinated monoalcohol was successfully linked to the HBPU end to form HBPUF. HBPUF latex possessed the core-shell particle structure and the favorable stability. Thermal stability of HBPUF film was enhanced by comparison with PU and HBPU films. The fluoroalkyl groups had the tendency to enrich at the film-air interface by XPS, which engendered water contact angle on HBPUF film increase from 77.8?on PU film to 113.9?and water absorption of HBPUF film reduce from 136.2% of PU film to 11.1%. Hydrophobicity of the HBPUF film was accordingly improved.