A photogalvanic cell was constructed using Nafion(R) and montmorillonite (MM) clay adsorbed [Ru(bpy)3]2+ coated electrodes in the presence of Fe3+ ions. Nafion(R) and MM clay adsorbed [Ru(bpy)3]2+ electrodes exhibited different photoelectrochemical behavior depending on the coating material. While anodic behavior was observed at a Nafion(R)-[Ru(bpy)3]2+ electrode with reference to an inert electrode in a photogalvanic cell, the MM clay-[Ru(bpy)3]2+ electrode showed cathodic polarity. A new photogalvanic cell was constructed by coating one electrode with Nafion(R)-[Ru(bpy)3]2+ and the other electrode with MM clay-[Ru(bpy)3]2+. This new photogalvanic cell showed an additive photogalvanic response on visible light irradiation.