Manganese oxides (MnOx) in alpha-, beta-, delta-MnO2 phases, Mn3O4, Mn2O3, and MnOOH are synthesized for systematically comparing their electrocatalytic activity of the oxygen reduction reaction (ORR) in the Zn -air battery application. The optimal MnOx/XC-72 mass ratio for the ORR is equal to 1 and the oxide crystalline structure effect on the ORR is compared. The order of composites with respect to decreasing the ORR activity is: alpha-MnO2/XC-72 > gamma-MnO2/XC-72 > beta-MnO2/XC-72 > delta-MnO2/XC-72 > Mn2O3/XC-72 > Mn3O4/XC-72 > MnOOH/XC-72. The textural properties of MnOx are investigated by scanning electron microscopy (SEM), transmission electron microscopy (TEM), N-2 adsorption/desorption isotherms with Brunauer-Emmett-Teller (BET) analysis, X-ray diffraction (XRD), and thermogravimetric analysis (TGA). Electrochemical studies include linear sweep voltammetry (LSV), rotating ring-disk electrode (RRDE) voltammetry, and the full-cell discharge test. The discharge peak power density of Zn-air batteries varies from 61.5 mW cm(-2) (alpha-MnO2/XC-72) to 47.1 mW cm(-2) (Mn3O4/XC-72). The maximum peak power density is 102 mW cm(-2) for the Zn-air battery with an air cathode containing alpha-MnO2/XC-72 under an oxygen atmosphere when the carbon paper is 10AA. The specific capacity of all full-cell tests is higher than 750 mAh g(-1) at all discharge current densities. (C) 2015 Elsevier B.V. All rights reserved.