The adsorption/transfer of the perfluorosulphonate ionomer Nafion(R) at the interface between two immiscible electrolyte solutions, (ITIES) is studied by cyclic voltammetry. The transfer of two adsorbed forms is observed and it is postulated that these two forms correspond to a morphological difference associated with the adsorption of Nafion(R) in the mixed solvent layer. Thermodynamic data are calculated for the two transferring forms. The observable transfer of the SO3CF3- (triflate) anion, which is structurally representative of Nafion(R)’s polymeric backbone, confirms the feasibility of the transfer process presented.