A novel procedure of anodic electrodeposition of copper oxides and hydroxides on glassy carbon and noble metals electrodes in an alkaline medium is described. The deposited films have been investigated by electrochemical and by X-ray photoelectron spectroscopy (\XPS) techniques. The copper films are deposited on the electrode surface as Cu(OH)(2) and CuO after the dissociation of the Cu(CN)(n)(1-n) complex caused probably by the formation of Cu-III species at relatively high applied potentials (i.e. 0.5 V). The resulting active copper films, independently of the electrochemical procedure adopted (i.e. potentiostatic or potentiodynamic conditions), appear to be uniform, smooth and with a good degree of adhesion on the electrode surface The electrocatalytic properties of the copper deposited films were investigated in an alkaline medium for the electrooxidation of several classes of organic compounds. (C) 2000 Elsevier Science B.V. All rights reserved.