 In this study, the electrochemical and anodic behaviors of MnO2/Pb anodes in electrowinning process were investigated. An accumulative roll-bonding (ARB) method was applied to fabricate MnO2/Pb nanocomposites. The electrochemical properties of the produced anodes were investigated by electrochemical impedance spectroscopy, cyclic voltammetry, electrowinning tests, and scanning electron microscopy. The results indicated that the ARB-process is an appropriate method to develop MnO2/Pb anodes. The produced anodes (Pb–0.5%MnO2-10pass samples) showed a 102% increase in current density compared to pure lead anode. The results of electrowinning tests revealed that Pb–0.5%MnO2-10pass samples had the best anodic performance with a significantly lower corrosion rate, product and electrolyte contamination, slime formation, energy consumption, and a higher current efficiency and consequently, a higher Zn deposition in cathode.