The lifetime and performance of a direct methanol fuel cell (DMFC) were investigated to understand the correlation between the structure of catalysts/membrane and cell performance versus time. The cell polarization and performance curves were obtained during the DMFC operation with the time. The catalysts and Nafion((R)) membrane of the membrane electrode assembly (MEA) from the lifetime test were comprehensively examined by XRD, HRTEM, FTIR and Raman spectroscopy techniques. The results revealed that there was significant performance degradation during the first 200 h operation; while the degradation was slowing down between 200 and 704 h operation. The degradation became worse after 1002 h operation. The increases of the catalyst particle size from both anode and cathode catalysts were observed after the DMFC lifetime test. The changes of microstructure, surface composition, the interfacial structure of the MEA, and the aging of Nafion((R)) under the DMFC lifetime tests were also observed. (c) 2006 Published by Elsevier Ltd.