In this study, the core-shell polymerization technique was employed to prepare the copolymer emulsions consisting of a polystyrene/acrylate core, whereas the shell was composed with fluoroacrylate. The parameters which influent the stability and properties of the emulsions, such as the reacting temperature, initiator type and its content, surfactants characteristics and their composition, and the monomer dosage mode, etc. were studied. Furthermore, the chemical structure of the copolymer and the morphology of the micelles were characterized by the methods of transmission electron microscopy (TEM), FTIR, and C-13-NMR. The surface properties of the latex films were characterized by the Dynamic Contact Angle Meter and Tensiometer (DCAT). Moreover, the relationship between the characteristics of emulsions and the water/oil repellency of the papers impregnated with the copolymer emulsions was studied as well.