A novel method to prepare well-dispersed Ni@Pd core-shell nanoparticles on multi-walled carbon nanotubes (Ni@Pd/MWCNTs) is reported. The morphology and crystallinity of the catalyst are characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD) analyses, respectively. Binary composite Ni@Pd/MWCNTs have been obtained and investigated for electrocatalysis of methanol oxidation in 0.5 M NaOH. It is observed that Ni@Pd/MWCNTs increases the apparent electrocatalytic activity and stability of the electrode considerably than that of PdNi/MWCNTs and Pd/MWCNTs catalysts. It is implied that Ni@Pd core-shell nanoparticles supported on MWCNTs is very promising for portable applications in DMFC in alkaline solution. (C) 2010 Professor T. Nejat Veziroglu. Published by Elsevier Ltd. All rights reserved.