Multifunctional sulfur-containing homo, block and random copolymers with a modulable number of noble metal affine groups were efficiently prepared by the atom transfer radical polymerization of S-(4-vinylbenzyl)thioacetate, in case with styrene. Their potential as model ligands for the stabilization of sub-5 nm noble metal nanoparticles is demonstrated through the one-step fabrication of well-controlled stable gold dispersions, in spite of working with a gold precursor to ligand concentration ratio considerably lower than those typically used in the presence of more traditional mono-functional terminated polymers.