A dipolar Ru(II) complex, [(bpy)2Ru(bpbh)Ru(bpy)2](ClO4)4 {where bpbh = 1,6-bis-[2-(2-pyridyl) benzimidazoyl]hexane, bpy = 2,2'-bipyridine}, was synthesized and characterized. A multilayer film of at least 18 layers was successfully prepared by alternating adsorption of H4SiW12O40 and [Ru2(bpy)4(bpbh)](ClO4)4 by electrostatic layer-by-layer self-assembly. The multilayer films were studied by ultraviolet-visible and X-ray photoelectron spectroscopy, atomic force microscopy, and cyclic voltammetry.