Poly[4-(2-aminoethyl)styrene], prepared by living anionic polymerization having n approximate to 18 repeat units and a molecular weight distribution of (M) over bar(w)/(M) over bar(n) = 1.10, has been derivatized by amide coupling to [Ru-II(vbpy)(2)(bpy-COOH)](2+) (vbpy is 4-vinyl-4’-methyl-2,2’-bipyridine; bpy-COOH is 4-methyl-2,2’-bipyridine-4’-carboxylic acid). A molecular model of the product, [PS-CH2CH2NHCO-(Ru-18(II))](36+), is shown at the left. Reductive electropolymerization based on the vinyl groups gives films having open, porous structures which retain the electron-transfer and excited-state properties of the constituent complexes but modified by the film environment.