The reaction mechanism of the electrooxidation of copper was investigated in alkaline solutions, from pH 12 to 14, using probe beam deflection. The application of this technique simultaneously with electrochemical experiments provides useful information concerning the chemical species formed from electrochemical as well as chemical reactions involved during the formation and dissolution of copper oxides. The concentration gradients at the electrode-electrolyte interface provide distinctive patterns showing significant changes in the corrosion behavior of the copper with increasing pH.