Reversible addition-fragmentation chain transfer (RAFT) is a versatile, controlled free radical polymerization technique that operates via a degenerative transfer mechanism in which a thiocarbonylthio compound acts as a chain transfer agent. The subsequent reduction of the dithioester end groups to thiols allows the preparation of (co)polymer-modified gold surfaces. Herein we report the immobilization of poly(sodium 4-styrenesulfonate), poly((ar-vinylbenzyl) trimethylammonium chloride), poly(N,N-dimethylacrylamide), and poly(3-[2-(N-methylacrylamido)-ethyldimethyl ammonio]propane sulfonate-b-N,N-dimethylacrylamide) onto gold films. The presence of the immobilized (co)polymers was confirmed by atomic force microscopy, attenuated total reflectance Fourier transform infrared spectroscopy, and surface contact angle measurements. The gold film modified with the block copolymer demonstrated stimuli-responsive behavior as evidenced by its water contact angle being similar to that of poly(N,N-dimethylacrylamide) even though the block based on 3- [2-(N-methylacrylamido)-ethyldimethyl ammonio] propane sulfonate was expected to be exposed to the aqueous environment.