Solid polymer electrolyte (SPE(R)) composite electrodes using a perfluorinated ion-exchange membrane (Nafion(R)), which is known to be microscopically separated into hydrophilic and hydrophobic domains, were prepared. Various N,N’-dialkyl-4-4’-bipyridinium salts (viologens) were incorporated in the SPE composite electrodes as phase transfer mediators. Electrochemical debromination of meso-1,2-dibromo-1,2-diphenylethane was carried out on the SPE composite electrodes. The results were compared with those obtained in an emulsion system consisting of water and dichloromethane. Of the viologen compounds tested, propyl viologen was the most effective mediator for the SPE composite electrode, while octyl viologen dibromide was the most effective mediator in the emulsion system. The active species for the debromination in the emulsion system was shown to be a doubly reduced neutral form of viologen that was generated by the disproportionation of cation radicals. The disproportionation constant, K(d), of octyl viologen cation radical in a two-phase system consisting of water and dichloromethane was estimated to be 809. The reaction mechanism on the SPE composite electrode was discussed, and it was considered that the active species was generated by disproportionation at the microscopically heterogeneous interface between the hydrophilic and hydrophobic domains of the Nafion.