A synthetic approach toward the synthesis of well-defined copolymers with attached phosphorescent iridium(III) emitters is presented. A reactive mu-hydroxy-bridged precursor complex has been utilized to coordinate suitable ligand sites of a methacrylate-based copolymer. The starting copolymer has been synthesized via the reversible addition fragmentation chain transfer (RAFT) polymerization technique. Using a reactive complex species, the coordination reaction at the copolymer could be performed under very mild conditions in the absence of any supporting additives.