A simple electrochemical approach is presented to quantitatively predict activation energy and mass transfer coefficient from a polarization curve of polymer electrolyte fuel cells to examine the membrane-electrode assembly(MEA) performance. It is assumed that the initial voltage drop at open circuit voltage is due to kinetic activation energy and that the current loss at short circuit current is due to mass transfer resistance. Accordingly, voltage drop in the activation polarization is converted into a change in the Gibbs free energy to determine the activation energy requirement. The mass transfer coefficient for current losses is derived from Fick’s law, based on the mass transfer limitation of oxygen at the oxygen reduction reaction sites. Case studies from the literature show reasonable correlations to the operating conditions, thereby providing a useful tool for prediction of the preliminary values of the activation energy and mass transfer coefficient for an MEA under various conditions.