We first prepared polymer-bound photoluminescent iridium complexes bearing a cyclometalated 2,2'-biphenylene ligand via an easy procedure in which the metallopolymer was synthesized by the reaction of a metal precursor with a polymer ligand. The iridium compound, [Ir(cod)(biph)Cl](2) (where cod and biph are 1,5-cyclooctadiene and biphenyl-2,2-diyl, respectively), was used as the iridium material, and a copolymer built by the radical copolymerization of 4-styryldiphenylphosphine and methyl methacrylate was employed as the polymer ligand. The obtained metallopolymers were highly crosslinked by iridium atoms forming P-Ir-P bonds. The content of the iridium was experimentally clarified to be in the range of 0.06-0.6 mmol/g of the polymer. Photoluminescence of the iridium polymer in the solid state was observed at 597 nm when the polymer was irradiated at 350 nm. As the Ir content in the copolymer increased to 0.2 mmol/g, the intensity of the luminescence also increased, but more iridium content decreased the intensity. Furthermore, the intensity of the photoluminescence in these photoluminescent polymers depended on the molecular weight of the copolymer ligands. (c) 2006 Wiley Periodicals, Inc.