Electropolymerization of the ligand-bridged, ruthenium polypyridyl assemblies [(vbpy)(2)ClRu(pz)-RuCl(vbpy)(2)](PF6)2 and [(bpy)(2)(CN)Ru(CN)Ru(vbpy)(2)(NC)Ru(CN)(bpy)(2))](PF6)(2) results in formation of electroactive thin films on Sn-doped indium oxide (ITO), Pt, and glassy-carbon electrodes. The assemblies retain their mixed-valence and photochemical properties in the films as shown below, for example, by the appearance of the Intervalence Transfer (IT) band for poly-[(bpy)(2)-(CN)Ru-II(CN)Ru-III(vbpy)(2)(NC)Ru-II(CN)(bpy)(2))](PF6)(3) on ITO in CD3CN.