In this study, we report the application of an inexpensive and easily prepared lead oxide–manganese oxide catalyst combined with Nafion (designated as Nf/PbMnO x ) as a highly efficient air-cathode for a zinc–air battery. We verify the mechanistic study of the reduction of O2 for Nf/PbMnO x in alkaline aqueous solution using rotating ring/disk electrode voltammetry, and also an electrochemical approach using a wall-jet screen-printed ring disk electrode. The presence of Nf/PbMnO x shows great catalytic activity for the disproportionation reaction of HO2 − to O2 and OH− with an overall 4e− reduction of O2 in the first reduction reaction. The 4e− reduction of O2 was eventually achieved at the Nf/PbMnO x through evidence from the slope of Koutecky–Levich plots. With these inherent features, we then fabricated the zinc–air battery with the Nf/PbMnO x catalyst and examine the performance for a practical application with air cathodes.