A solid state photoelectrochemical bilayer cell was fabricated with Ru(bpy)(3)(2+) + PEG + Nafion layer and MV2+ pendant polysiloxane (PSiO-MV2+) layer. The effect of PEG addition on the photoelectric properties was discussed especially with charge transport in the Nafion layer. Increase in photoelectric properties produced by PEG addition to the Nafion layer was found for the solid state cells. Solid state voltammetry indicated that this increase was attributed to the increase in D-app for Ru(bpy)(3)(2+) in the Nafion layer. From emission lifetime of Ru(bpy)(3)(2+) in the Nafion film, spatial distribution and local motion of the Ru(bpy)(3)(2+) molecules in the Nafion film were estimated to analyse charge transport process, physical diffusion and/or electron hopping, in detail. As a result, PEG addition would affect the electron hopping reaction between Ru(bpy)(3)(2+) and Ru(bpy)(3)(3+) molecules in the Nafion film, resulting in the increase in photoelectric properties for the cell containing PEG.