Supramolecular block-random copolymers containing [Ir(terpy)(2)](3+) in the side chain were synthesized via postfunctionalization of a P(S-b-AC(terpy)) block copolymer. Absorbance and emission spectra compared to a model compound show that the polymer backbone has a minor effect on the polymer absorbance but produces a larger shift for the phosphorescence signals to higher wavelength. Dynamic light scattering of the metal complex containing copolymer studied in various solvents showed monomodal aggregation with decreasing aggregate size as the solvent dielectric constant increased. The copolymer precursor P(S-b-AC(terpy)) shows multimodal aggregation in different solvents with the major population consisting of single chains. This difference in behavior between the two polymers is attributed to the electrolytic nature of the complex and the amphiphilicity induced by the charged metal complex. Supramolecular copolymers like these will continue to have interesting self-organizational properties and may find applications in multicomponent systems for photoinduced charge separation processes. (c) 2006 Wiley Periodicals, Inc.