A PtPb alloy catalyst with a uniform core-shell structure was synthesized in a two-step rapid microwave-assisted polyol process. The X-ray diffraction (XRD) and transmission electron microscopy (TEM) data demonstrate that the core of this catalyst is a Pt particle, and the shell or completely alloyed nanoparticles are composed of a PtPb alloy with an hcp structure. The average diameter of the catalyst is approximately 5.9 nm. The PtPb alloy catalyst exhibits enhanced catalytic activity and durability for methanol or formic acid oxidation. The anodic peak current densities for methanol oxidation at the 950th cycle on PtPb/C, PtRu/C (JM) and Pt/C (JM) catalysts are 870.6, 596.4 and 472.9 mA mg(-1) Pt, respectively. The formation of large numbers of oxides on the PtPb/C catalyst surface can enhance the anti-poisoning ability and catalytic durability of the catalyst. (C) 2012 Elsevier Ltd. All rights reserved.