Electrochemical oxygen reduction reaction (ORR) during discharge and oxygen evolution reaction (OER) during charge are the key electrode processes for rechargeable metal–air batteries. In this article, we report a high-performance self-supported AuNi-Cu2O hybrid, which works as a bi-functional electrocatalyst for ORR and OER. The as-prepared AuNi-Cu2O hybrid exhibits excellent catalytic activity, the ORR activity of which is superior to that of commercial Pt/C, and the OER activity of which is close to that of commercial IrO2/C. Moreover, AuNi-Cu2O hybrid exhibits better durability than commercial Pt/C and IrO2/C. The excellent catalytic performance of AuNi-Cu2O could be attributed to the increase of active sites and the strong “mutual” interaction between Au and Ni induced by leaching of Cu2O.