PtRu/C and PtRu black catalysts with nominal Pt:Ru atomic ratio of 1:1 are prepared by a modified polyol process (co-reduction of metal precursor salts) as anode catalysts for direct methanol fuel cells (DMFCs). Without the carbon support, PtRu nanoparticles tend to agglomerate, while the PtRu nanoparticles in PtRu/C have a good dispersion as shown by TEM. Both PtRu black and PtRu/C have the almost same alloy degree indicated by XRD, but PtRu supported on carbon could improve the influence of Ru on Pt toward methanol oxidization as shown by cyclic voltammetry. The microstructure of PtRu/C is further studied by high-resolution transmission electron microscopy (HRTEM), and the results indicate that the lattice constant of Pt in PtRu electrocatalyst has contracted despite a few parts of Pt not alloyed with Ru due to the lattice constant of Pt without contracting, which is further proved by the results of temperature-programmed reduction (TPR). Such parts of unalloyed Ru are further proved to have ability to reduce the methanol oxidation potential on Pt by comparing the catalytic behaviors of Pt/C and Pt + Ru/C prepared by mixing carbon with separately prepared Pt and Ru colloids. Moreover, the catalytic behaviors of PtRu black and PtRu/C are also compared with those of commercial ones. (C) 2007 Elsevier B.V All rights reserved.