Design of novel nano-scale catalysts with high activity and low cost for methanol oxidation reaction is crucial for the development of direct methanol fuel cell. In this study, MnOx Pt and Pb were forced to precipitate successively on the surface of carbon nanotubes for fabricating a PtPb/MnOx-CNTs catalyst. Physical characterizations indicated that there existed a mass of Mn (IV, V), Pb (II) and Pt (0) species, and partial alloying between Pt and Pb in this catalyst. Methanol oxidation reaction with this novel composite exhibited over 3 times higher specific activity (140.9 mA cm(-2)) and somewhat lower onset potential (-0.1 V vs. Hg/Hg2SO4) than the values on Pt/CNTs (44.2 mA cm(-2) and 0 V, respectively). Fundamental understanding in reaction mechanisms enabled us to reveal the distinguishing functions between Pb and MnOx in methanol oxidation processes. The addition of Pb resulted in the enhanced intrinsic activity towards electro-oxidation of residual intermediate species, while dehydrogenation in methanol oxidation processes was obviously improved by using MnOx-CNTs as a support. Copyright (C) 2011, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.