Polystyrene-b-poly(4-vinylpyridine) copolymers were quaternized with 1-bromohexane and 6-perfluorooctyl-1-bromohexane. Surfaces prepared from these polymers were characterized by contact angle measurements, near-edgeX-ray absorption fine structure spectroscopy and X-ray photoelectron spectroscopy. The fluorinated pyridinium surfacesshowed enhanced antibacterial activity compared to their nonfluorinated counterparts. Even a polymer with a relativelylow molecular weight pyridinium block showed high antimicrobial activity. The bactericidal effect was found to berelated to the molecular composition and organization in the top 2−3 nm of the surface and increased with increasinghydrophilicity and pyridinium concentration of the surface.