Exposure of thin Nafion layers to 300 keV electron beam irradiations has a remarkable effect on the properties of adsorbed Ru(bpy)(3)(2+) and methyl viologen (MV(2+)) ions. Irradiation, both in the presence and in the absence of the adsorbants, shows a pronounced effect on slowing charge migration rates. Irradiation in the presence of Ru(bpy)(3)(2+) induces a red shift in the emission band. The results are interpreted in terms of radiation-induced cross-linking and covalent binding of Ru(bpy)(3)(2+) and MV(2+) to the Nafion chains. Both mobile and immobile Ru(III) slowly oxidize bpy ligand. Immobilization of the Ru complex explains also photochemical results.