Cationic polyurethane‐fluorinated acrylate hybrid dispersions (PUFA) were prepared by the copolymerization of styrene, butyl acrylate, and 2,2,3,4,4,4‐hexafluorobutyl methacrylate in the medium of crosslinked polyurethane via phase inversion polymerization. The said polyurethane was synthesized in acetone from 2,4‐tolyene diisocyanate, N‐methyldiethanolamine, trimethylolpropane, and soft polyester diol block. The influences of hydrophilic monomer on the surface properties, immersion behaviors, particle size and, zeta potential of the dispersions were investigated. The results show that the addition of hydrophilic monomer can be advantaged to the stability of dispersions and yet will increase the surface free energy by more than 19.9%. The PUFA coating films cured at ambient conditions have the lower surface free energy (less than 0.02033 J/m2). At the same time, there is an obvious mobility of fluorinated groups in fluorinated polymer films. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006