Nanorods with an α type MnO(2) structure and a diameter ranging from 25 to 40 nm, along with tipped needles with a β MnO(2) structure and a diameter of 100 nm were obtained. The 25 nm diameter α MnO(2) nanorods showed the best catalytic activity for dissociation of HO(2)(-) formed during oxygen reduction in a KOH solution. The MnO(2) nanostructures preferably followed a two-electron oxygen reduction mechanism in a LiOH solution. The size of the catalyst also affected the specific capacities of the non-aqueous Li/O(2) batteries fabricated using the MnO(2) based air electrode. The highest specific capacity of 1917 mA h g(-1) was obtained for an α MnO(2) nanorod catalyst having a diameter of 25 nm. The cation present in the MnO(2) nanostructures appears to determine the catalytic activity of MnO(2).