In this paper, nano Ag4Bi2O5/rGO composite catalyst was obtained by in-situ growth and co-precipitation. The nano Ag4Bi2O5 with a length of 200-300 nm and a width of 10-20 nm is supported by the surface of reduced graphene oxide. The obtained catalyst was represented by SEM, XRD, XPS, EDS and TG-DTG methods, and its electrocatalytic properties were evaluated by RDE, linear sweep voltammetry, EIS and cyclic voltammetry tests. The CV results display that there is a significant oxygen reduction peak current (2.27 mA cm(-2)) at the potential of 0.82V in the oxygen saturated 0.1 mol L-1 KOH electrolyte. The LSV result shows, the catalyst has slightly higher current density (4.96 mA cm(-2)) and half-wave potential (0.75 V) than commercial Pt/C through a 4 electrons oxygen reduction mechanism. The results of i-t chronoamperometric method show the catalyst has superior methanol tolerance ability to the commercialized Pt/C (20%). Furthermore, the assembled Zn-O-2 batteries with Ag4Bi2O5/rGO oxygen electrode provide better durability performance than commercialized Pt/C (20%) in the same alkaline electrolyte. (C) 2019 The Electrochemical Society.