We report the preparation of well-dispersed Pt nanoparticles depositing on Mn3O4-modified multi-walled carbon nanotubes (Mn3O4-MWCNTs) that can be taken as high performance catalyst in methanol electro-oxidation. Various spectrometry techniques such as FT-IR, Raman, XRD, TEM and XPS measurements were performed, revealing that the Pt nanoparticles were highly dispersed on the surface of Mn3O4-modified MWCNTs with a narrow size distribution between 1.7 nm and 3.9 nm. Compared the Pt/MWCNT catalyst without Mn3O4 modification, the Pt/Mn3O4-MWCNT composite catalyst not only shows relative large electrochemical active surface area (EAS), high catalyzing activity toward methanol electro-oxidation, but also exhibits very high stability with apparent anti-poisoning tolerance to the incomplete oxidized species during methanol oxidation. Copyright (c) 2012, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.