We here report on very high capacity (11,000 mA h g(-1)), superb rate capability (4500 mA h g(-1) at 5000 mA g(-1)) and high reversibility of Li-air batteries using α-MnO2 NW catalysts mainly associated with their relatively large amount of Mn(3+) exposed on the NW surface and a unique mechanism for deposition of discharge products. Our findings of the unprecedentedly fast Li ion transport and reversible formation-decomposition of discharge products attributed to the modified surface arrangement of α-MnO2 NWs suggest a strategy for achieving high-power Li-air batteries in combination with nano-architecture tailoring.