The ligand derivative, 4,4'-bis(chloromethyl)-2,2'-bipyridine (bpy(CH2Cl)(2)), and Ru(II) complexes with 2, 4, or 6 pendant halomethyl groups were employed as initiators in the atom transfer radical polymerization (ATRP) of styrene to produce linear and star polymers with ligands and chromophores at discrete positions in the polymer architectures. With the metalloinitiators, [Ru(bpy)(n)-{bpy(CH2Cl)(2)}(3-n)](PF6)(2) (n = 0, 1, 2), styrene polymerizations were run in bulk monomer, as well as in the presence of small amounts of anisole (14% v/v vs styrene), employing either CuCl/2bpy(C13H27)(2) or CuBr/1,1,4,7,10,10-hexamethyltriethylenetetraamine (HMTETA) as the ATRP catalyst. Kinetics experiments were performed to determine the level of molecular weight control that is attainable in these polymerizations. With the former catalyst and when anisole is added, reactions exhibited increased control for the metalloinitiators and ligand initiators. Since the dicationic metalloinitiators exhibited limited solubility, which correlated with poor initiation, attempts were made to improve the compatibility of metalloreagents in the nonpolar ATRP medium. Di- and tetrafunctional metalloinitiators modified with alkyl chains, [Ru{bpy(C13H27)(2)}(n){bPY(CH2Cl)(2)}(3-n)](PF6)(2) (n = 1, 2), displayed improved initiation and molecular weights closer to targeted values. However, attempts to improve the solubility of the homoleptic complex, [Ru{bpy(CH2Cl)(2)}(3)](PF6)(2) by substituting a BAr4'-counterion for PF6- did not enhance molecular. weight control. The use of DMF, a more polar solvent, in place of anisole did increase solubility of the hexafunctional initiator; at low monomer conversion, polydispersities were lower in DMF vs anisole. Polymers were characterized by gel permeation chromatography (GPC) with refractive index (RI) and multiangle laser light scattering (MALLS) detection, by UV/vis spectroscopy to confirm the covalent attachment of Ru(II) chromophores to polystyrene chains, and by modulated differential scanning calorimetry (MDSC).