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In this work, copper(II) hydroxide (Cu(OH)2) and copper oxide (Cu2O) nanostructures are deposited on functionalized multi-walled carbon nanotubes/polypyrrole to report an efficient electrocatalyst for ethanol oxidation in alkaline medium. In the first step, the deposition of functionalized multi-walled nanotubes of carbon (F-MWCNTs) on the electrode surface was carried out using drop casting mode followed by the electrodeposition of polypyrrole (PPy) and copper nanoparticles (Cu-Nps) using galvanostatic mode. Scanning electron microscopy (SEM) and X-ray diffraction (XRD) were performed in order to study the morphology and the structure of the elaborated catalysts. Electrochemical characterization conducted by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) revealed that the introduction of functionalized multi-walled carbon nanotubes enhances the electric properties of the nanocomposites and offers a large active surface area. The prepared electrocatalyst was then tested in a solution of 0.1 M NaOH containing 0.2 M of ethanol showing high performance (7 mA cm−2 at 0.85 V vs Ag/AgCl) and good stability (over 1800 s) toward ethanol oxidation.