This study was motivated by the need for improved understanding of the kinetics and transport phenomena in a homogeneous catalyst system for the oxygen reduction reaction (ORR). Direct interaction between the sulfonic groups of Nation and an Fe(III) meso-tetra(N-methyl-4-pyridyl) porphine chloride (Fe(III)TMPyP) compound was observed using FTIR and in situ UV-Vis spectroelectrochemical characterizations. A positive shift of the half wave potential value (E-1/2) for ORR on the iron porphyrin catalyst (Fe(III)TMPyP) was observed upon addition of a specific quantity of Nation ionomer on a glassy carbon working electrode, indicating not only a faster charge transfer rate but also the role of protonation in the oxygen reduction reaction (ORR) process. A membrane electrode assembly (MEA) was made as a sandwich of a Pt-coated anode, a Nafion (R) 212 membrane, and a Fe(III)TMPyP + Nation ionomer-coated cathode. This three-dimensional catalysis system has been demonstrated to be working in a H-2/O-2 proton exchange membrane (PEM) fuel cell test. Published by Elsevier B.V.