The electrochemical and Raman spectroscopic characteristics of propylviologen incorporated into Nafion(R) film coated on a silver electrode were studied. The results were compared with those on silver in solutions containing Triton X-100, cetyltrimethylammonium bromide (CTAB) and sodium dodecyl sulfate (SDS) micelles. Propylviologen incorporated into Nafion(R) showed unusual electrochemical and Raman spectroscopic behavior. The half-wave potential for the second step was shifted in the negative direction with respect to that in an aqueous solution, and only a small amount of the doubly reduced form was detected by Raman spectroscopy. Similar behavior was observed in the anionic SDS micellar solution. On the basis of the observed similarity, the residence sites of propylviologen in Nafion(R) were discussed.