Ag-MnOx/C composites were prepared using AgNO3 and KMnO4 as the precursors and Vulcan XC-72 as the support. The physical properties of the Ag-MnOx/C composites were investigated via X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM). The activity and the stability of the series of Ag-MnOx/C composites toward the oxygen reduction reaction (ORR) in alkaline media were investigated through the electrochemical techniques. The results show that the main species MnO2 and Ag2O in the fresh sample convert into Mn3O4 and Ag(0), respectively, after the heat treatment in N2 at 300°C (Ag-MnOx/C-300). The Ag-MnOx/C-300 sample shows the highest activity toward the ORR, with the half-wave potential of the ORR shifting negatively only 0.035V compared to that on the commercial 40wt. % Pt/C (JM). The electron transfer number during the ORR on the Ag-MnOx/C composite increases with the value close to four after the heat treatment at 300°C, which is mainly attributed to the formation of Ag(0), rather than Mn3O4. The heat treatment brings about a better catalytic stability of the composite, and no obviously negative shift takes place for the half-wave potential of the ORR on the Ag-MnOx/C-300 composite after 1000 cycles accelerated aging test. The maximum power density of the zinc-air battery with the Ag-MnOx/C-300 air electrode reaches up to 130 mW cm−2, higher than those based on the Pd/C and Pt/C cathode catalysts, which shows that the Ag-MnOx/C-300 composite is a promising candidate as the catalyst for the air electrode.