By using metal ions as templates for polymer synthesis, functional materials with a wide range of molecular architectures may be readily generated. Polystyrene macroligands, bpyPS and bpyPS(2), with bipyridine (bpy) donors at the end and center of the chain, respectively, were generated by copper-catalyzed atom transfer radical polymerization (ATRP). Heteroleptic polymeric Ru(TI) tris(alpha -diimine) complexes were prepared by combining nonpolymeric ligands and polymeric bpyPS(n) ligands of different molecular weights. The reaction of bpyPS(2) with Ru(DMSO)(4)Cl-2 in CHCl3 solution to form a putative [Ru(bpyPS(2))(DMSO)(m)Cl-2](2+) intermediate, followed by dehalogenation with AgPF6 in the presence of excess 2,2'-bipyridine, led to linear polymeric complexes, [Ru(bpyPS(2))(bpy)(2)](2+). More versatile were sequences involving chelation of 2 equiv of a bpyPS(n), followed by association of another polymeric or nonpolymeric ligand with the Ru(II) center. Ruthenium-centered linear polymers, [Ru(bpyPS)(2)(L)](2+) (L = bpy or 4,4'-bis(hydroxymethyl)-2,2'-bipyridine), and analogous four-arm stars, [Ru(bpyPS(2))(2)(L)](2+) (L = bpy, 1,10-phenathroline, 4,4'-bisihydroxymethyl)-2,2'-bipyridine, and 4,4'-bis(tricosanyl)-2,2'-bipyridine) were prepared in this fashion. Reactions forming [Ru(bpyPS(n))(2)Cl-2] and [Ru(bpyPS(n))(2)(solvent)(m)](2+) intermediates showed a marked molecular weight dependence. In certain cases, reactivity at the Ru center could be modulated by changing the polarity of the reaction media (DME vs DME/MeOH). Differences in the conformation of polystyrene chains in different solvents were exploited as a "protecting group" strategy in polymeric metal complex synthesis. By using two different kinds of bpyPS(n) macroligands, home-block copolymer Ru-centered stars, [Ru(bpyPS)(2)(bpyPS(2))](2+) and [Ru(bpyPS(2))(2)(bpyPS)](2+), were generated. GPC and UV/vis spectroscopy confirm that the Ru(II) chromophores are associated with eluting polymer fractions and allow for comparison of relative chelation efficiencies.