Lead oxidation and subsequent oxygen evolution have been studied in a zinc electrowinning solution employing cyclic voltammetric and real-time Fourier transform electrochemical impedance spectroscopy (FTEIS) experiments. A large body of impedance data obtained as a function of scanned potential by running combined staircase cyclic voltammetry and FTEIS experiments led to systematic analysis on the electrode/electrolyte interface. The changes in solution resistances, film resistances as well as film capacitances, double layer capacitances, polarization resistances, and Warburg admittances observed during lead oxidation satisfactorily explain corresponding electrochemical reactions. Various electrode reaction kinetic parameters for oxidation of lead and oxygen evolution were obtained from the impedance data. The reaction mechanism is discussed based on the impedance data. (C) 2012 Elsevier Ltd. All rights reserved.