Poly(ethylene glycol) (PEG) is often used to biocompatibilize surfaces of implantable biomedical devices. Here, block copolymers consisting of PEG and l-cysteine-containing poly(amino acid)s (PAA's) were synthesized as polymeric multianchor systems for the covalent attachment to gold surfaces or surfaces decorated with gold nanoparticles. Amino-terminated PEG was used as macroinitiator in the ring-opening polymerization, (ROP), of respective amino acid N-carboxyanhydrides (NCA's) of l-cysteine (l-Cys), l-glutamate (l-Glu), and l-lysine (l-Lys). The resulting block copolymers formed either diblock copolymers, PEG-b-p(l-Glu(x)-co-l-Cys(y)) or triblock copolymers, PEG-b-p(l-Glu)(x)-b-p(l-Cys)(y). The monomer feed ratio matches the actual copolymer composition, which, together with high yields and a low polydispersity, indicates that the NCA ROP follows a living mechanism. The l-Cys repeat units act as anchors to the gold surface or the gold nanoparticles and the l-Glu repeat units act as spacers for the reactive l-Cys units. Surface analysis by atomic force microscopy revealed that all block copolymers formed homogenous and pin-hole free surface coatings and the phase separation of mutually immiscible PEG and PAA blocks was observed. A different concept for the biocompatibilization of surfaces was followed when thiol-terminated p(l-Lys) homopolymer was first grafted to the surface and then covalently decorated with HOOC-CH2-PEG-b-p(Bz-l-Glu) polymeric micelles. (c) 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014, 52, 248-257