A series of polystyrene (PS) copolymers containing 2,3,4,5,6-pentafluorostyrene units with different monomer ratios were prepared for antifouling applications. PS, poly(styrene-co-pentafluorostyrene) (poly(S-co-FS)), and poly(pentafluorostyrene) (PFS) were synthesized by free-radical polymerization and characterized by 1H NMR, Fourier-transform infrared spectroscopy, and gel permeation chromatography. The surface energy of the polymer films decreased with increasing content of fluorinated styrene. Protein adsorption experiments were carried out on the synthesized polymer films using fluorescein isothiocyanate-labeled bovine serum albumin as a fluorescent protein. The photo-luminescence intensity of the protein-adsorbed polymer films decreased dramatically as the content of hydrophobic fluorinated styrene increased, suggesting that poly(S-co-FS) copolymers and PFS could be used as potential antibiofouling coatings.