Carbon-supported PtPb intermetallic compound (PtPb/C) is prepared by modified polyol method, and its electrochemical performance for methyl formate electrooxidation is investigated by half cell and single cell tests in comparison with commercial Pt/C and PtRu/C catalysts. In half cell operation at low potentials below 0.4 V. the dominant reaction is the oxidation of formic acid produced by acid-catalyzed hydrolysis of methyl formate, and PtPb/C exhibits the highest activity. At higher potentials, methanol joins the oxidation process of methyl formate and PtRu/C shows the high activity. In single cell operation, PtPb/C shows the highest performance for electrooxidation of methyl formate and could become a practical anode electrocatalyst for direct methyl formate fuel cells. (C) 2011 Elsevier B.V. All rights reserved