The electrochemical oxidation of 3,4-(methylenedioxy)phenylmethanol (piperonyl alcohol) was characterized by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). Two electrochemical oxidation signals were found for piperonyl alcohol. The authors propose that the first oxidation wave corresponds to the formation of radical cation species, which is consumed by a fast chemical reaction with water. The final products of this reaction are piperonal and other products. The second oxidation wave, which appears at more positive potentials, corresponds to piperonal oxidation. The heterogeneous rate constant, the transfer coefficient for the first electrochemical oxidation reaction and the diffusion coefficient of the alcohol were determined in the present work by digital simulations. The passivation process of the electrode at positive potential was characterized by EIS.