The electrochemical and photonic properties of a metallopolymer in which both [Ru(dpp)(2)Cl](+) (N5Cl) and [Ru(dpp)(2)](2+) (N6) moieties are coordinated to a poly(4-vinylpyridine) backbone are described, dpp is 4,7diphenyl-1,10-phenanthroline. Cyclic voltammetry and luminescence studies indicate that approximately 2% of centres are bis-coordinated to the PVP backbone, i.e., 2% are [Ru(dpp)(2)](2+). When dissolved in ethanol or acetonitrile, two photolurninescence peaks are observed, at 620 and 720 nrn corresponding to the N6 and N5CI moieties, respectively. This dual emission indicates that the two centres communicate weakly in solution. In contrast, in aqueous solution or in thin films, a single emission band at 720 nm is observed suggesting efficient energy transfer to the N5Cl moiety. Polymer films generate electrochemiluminescence in the presence of oxalate as a co-reactant with an emission maximum at 730 nm corresponding to emission from the N5Cl centres alone. (c) 2008 Published by Elsevier B.V.