The effect of water on polymer electrolyte fuel cell degradation was examined with humidity as a parameter. Polymer electrolyte fuel cells were subjected to long-term operation of 10 000 h to examine the relation between decline in cell voltage and degradation of the catalyst layers or gas diffusion layers. The diffusion overpotential increased during long-term operation at relatively high humidification of 81% RH, but only in the catalyst layer and not in the gas diffusion layer. At low humidification of 52% RH, the increase in diffusion overpotential was small, indicating that the increase was more likely to occur under high humidification. Post-analysis of the catalyst layer revealed that the membrane electrode assembly had increased diffusion overpotential during operation under high humidification, as a result of the sharp decline in porosity. The increase of diffusion overpotential in the catalyst layer was also investigated by the observation of the degradation due to the oxidation of the Pt-carbon supports. However, it was found that the oxidation of carbon support which had increased diffusion overpotential was small. (C) 2009 Elsevier B. V. All rights reserved.