Core-shell like behavior has been shown by the nanoparticles comprised of Pd and Mo that have been synthesized on multiwall carbon nanotubes (Mo@Pd/MWCNT or Pd@Mo/MWCNT) by hydrothermal technique in different pH. The synthesized catalysts are characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDS) and X-ray photoelectron spectroscopy (XPS). The formation mechanism of the core-shell like PdMo nanoparticles has been explained with the consequences of reduction potential and surface segregation properties of Pd and Mo. The activity of the catalysts towards methanol oxidation is investigated by cyclic voltammetry (CV), chronoamperometry and impedance spectroscopy. The primary electrochemical analysis indicates that the electrochemical activity of this Pd@Mo/MWCNT along with Mo@Pd/MWCNT is better than that of Pd/MWCNT. Copyright (C) 2012, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.