Coordination of nitric oxide (NO) to meso-tetraphenylporphyrin cobalt in solutions containing methanol and in Nafion((R)) film has been studied by cyclic voltammetry, visible spectroscopy, ESR and FTIR. Formation of (CoTPP)-T-II(NO) has been observed in the alcoholic solutions of both Co-II- and Co-III-complexes in the presence of NO. The same reductive nitrosylation has been observed only for (CoTPP+)-T-III distributed in the hydrophobic part of the Nafion((R)) film. The electrochemical oxidation of the resulting NO-complex in the methanolic solution and in Naflon((R)) film has been monitored, and demonstrated the catalytic character under an excess of NO. A reaction scheme for the catalytic process, which includes reductive nitrosylation followed by oxidation of (CoTPP)-T-II(NO) has been suggested. A possible role of trace amount of alcohols in the Nafion((R)) film has been discussed.