A water-soluble polyanionic polyacrylate was rendered electroactive by the covalent attachment of (on average) one ferrocene molecule to each polymer chain. Electro-oxidation of the ferrocene labels produced ferricinium groups that could not be electro-reduced in dilute supporting electrolyte solutions (less than 0.1M). However, Ru(NH3)(6)(3+) counterions bound electrostatically to the oxidized polyanion could be electro-reduced and the resulting, bound Ru(NH3)(6)(2+) counterions rapidly reduced the ferrocenium groups on the same polyanionic chain by intramolecular electron transfer. These phenomena are demonstrated by means of cyclic voltammetry. Experimental and numerically simulated cyclic voltammetric responses are compared to support the mechanism proposed to account for the observed results which may be relevant to long range electron transfers in redox enzymes and across molecular monolayers on surfaces.