Due to the poor electric conductivity but the excellent catalytic ability for the oxygen reduction reaction (ORR), manganese dioxide in the α phase (denoted as α-MnO2) anchored onto carbon black powders (XC72) has been synthesized by the reflux method. The specific surface area and electric conductivity of the composites are generally enhanced by increasing the XC72 content while the high XC72 content will induce the formation of MnOOH which shows a worse ORR catalytic ability than α-MnO2. The ORR activity of such air cathodes have been optimized at the XC72/α-MnO2 ratio equal to 1 determined by the thermogravimetric analysis. By using this optimized cathode under the air atmosphere, the quasi-steady-state full-cell discharge voltages are equal to 1.353 and 1.178 V at 2 and 20 mA cm−2, respectively. Due to the usage of ambient air rather than pure oxygen, this Zn-air battery shows a modestly high discharge peak power density (67.51 mW cm−2) meanwhile the power density is equal to 47.22 mW cm−2 and the specific capacity is more than 750 mAh g−1 when this cell is operated at 1 V.