In this work, for the first time, a novel and facile method for preparation of highly porous poly (o-Anisidine) (POA) by two-step process, through electropolymerization after electrochemical pretreatment of carbon paste electrode (CPE) is reported. Electrochemical response of the prepared POA at the surface of electrochemically pretreated CPE (pCPE) is, at least, 12 times higher than that obtained at the CPE. Copper (Cu) nanoparticles are uniformly electrodeposited onto the POA/pCPE composite. Then, platinum (Pt) nanoparticles are prepared through spontaneous and irreversible reaction via galvanic replacement between [PtCl6](2-) ions and the Cu nanoparticles. The prepared bimetallic Pt/Cu nanoparticles are characterized by scanning electron microscopy (SEM), energy dispersive spectroscopy and electrochemical methods. Electrochemical impedance spectroscopy shows that on the pCPE, charge transfer resistance is much smaller than that the CPE. The SEM images reveal that the electrochemical pretreatment of the CPE strongly influences morphology of the polymer film. The methanol oxidation and stability of the Pt-Cu/POA/pCPE are investigated by various electrochemical techniques. The results indicate that the modified electrode exhibits excellent electrocatalytic activity towards methanol oxidation. Copyright (C) 2014, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.