The electrocatalytic oxidation of methanol was studied on Ni-P and Ni-Cu-P supported over commercial carbon electrodes in 0.1 M KOH solution. Cyclic voltammetry and chronoamperometry techniques were employed. Electroless deposition technique was adopted for the preparation of these catalysts. The effect of the electroless deposition parameters on the catalytic activity of the formed samples was examined. They involve the variation of the deposition time, pH and temperature. The scanning electron micrography showed a compact Ni-P surface with a smooth and low porous structure. A decreased amount of nickel and phosphorus was detected by EDX analysis in the formed catalyst after adding copper to the deposition solution. However, an improvement in the catalytic performance of Ni-Cu-P/C samples was noticed. This is attributed to the presence of copper hydroxide/nickel oxyhydroxide species. It suppresses the formation of gamma-NiOOH phase and stabilizes beta-NiOOH form. Linear dependence of the oxidation current density on the square root of the scan rate reveals the diffusion controlled behaviour. (C) 2009 Professor T. Nejat Veziroglu. Published by Elsevier Ltd. All rights reserved.