Exploring Pt-free electrocatalysts with high activity and long durability for the oxygen reduction reaction (ORR) has been long pursued by the renewable energy materials community. In this work, we have designed an ordered intermetallic PdZn/C (O-PdZn) with a several atomic-layer Pd shell, which achieved a 3-fold enhancement in ORR mass activities (MA) in alkaline media, relative to Pd/C and Pt/C. Further Au incorporation in O-PdZn/C (Au-O-PdZn/C) yielded a catalyst with superior durability with less than 10% loss in MA after 30000 potential cycles. These effects have attributed to the rationally designed ordered structure and stabilizing effect of Au atoms. Aberration-corrected scanning transmission electron microscopy and synchrotron-based X-ray fluorescence spectroscopy were employed to show that Au not only galvanically replaced Pd and Zn on the surface but also penetrated through the PdZn lattice and distributed uniformly within the particles. Au-O-PdZn/C was also tested as an effective oxygen cathode in broad applications in rechargeable Li–air and Zn–air batteries.