In the present paper, the effect of electrode preparation procedure on the structural properties of membrane electrode assembly (MEA) and consequently on the performance of direct methanol fuel cells (DMFCs) was investigated. Commercial PtRu black anode catalyst and Pt black cathode catalyst were characterized by XRD in their initial form and in their intermediate and final states after each step involved in catalyst-coated membrane electrode preparation procedure by a decal transfer method (DTM). XRD results demonstrated that the DTM process has a significant effect on the catalyst structural properties, especially on the particle size of Pt black cathode catalyst. It is also discussed that among all the steps involved in the electrode fabrication procedure, catalyst ink preparation and high temperature transfer process are key factors affecting the particle size of Pt black catalyst. Furthermore, it was found that the maximum power density of the single DMFC using a MEA fabricated by the DTM, when air is used as oxidant, is more than two times greater than that of the cell using conventionally prepared MEA, and more than three times greater when pure oxygen is used as oxidant. This could be attributed to the easier mass transportation due to the thinner catalyst layer and the better contact between the catalyst layer and the electrolyte membrane in the former case, even if, according to in situ CO stripping voltammetry results in the fuel cell anode environment, the surface composition of PtRu anode has been changed. (c) 2005 Elsevier B.V. All rights reserved.