To study the coupled phenomena occurring in proton exchange membrane fuel cells, a two-phase, one-dimensional, non-isothermal model is developed. The model includes water phase change, proton transport in the membrane and electro-osmotic effect. The thinnest, but most complex layer in the membrane electrode assembly, catalyst layer, is considered an interfacial boundary between the gas diffusion layer and the membrane. Mass and heat transfer and electro-chemical reaction through the catalyst layer are formulated into equations, which are applied to boundary conditions for the gas diffusion layer and the membrane. Detail accounts of the boundary equations and the numerical solving procedure used in this work are given. The polarization curve is calculated at different oxygen pressures and compared with the experimental results. When the operating condition is changed along the polarization curve, the change of physicochemical variables in the membrane electrode assembly is studied. In particular, the over-potential diagram presents the usage of the electro-chemical energy at each layer of the membrane electrode assembly. As the fuel cell reaction becomes more limited by mass transfer, it is found that higher over-potential is uselessly concentrated on the cathode catalyst layer. The over-potential for the anode reaction was usually ignored in other studies, but the ratio of the anode over-potential to the cathode over-potential increases at a higher current condition. Water content is distributed more unevenly in the membrane, as the cell current is increased. That causes the proton conductivity of membrane to decrease and the water content to increase in the cathode side, which hampers 02 transfer. The effect of electro-osmotic property, one of important property of membrane, on cell performance is also studied. (C) 2011 Elsevier Masson SAS. All rights reserved.