Rechargeable lithium–air battery is studied using Pd/mesoporous α-MnO2 air composite electrode. In the present work, we have studied the preparation and electrochemical performance of ordered mesoporous α-MnO2 as a cathode catalyst for rechargeable Li–air batteries. α-MnO2 was prepared by reduction of KMnO4 solution in acidic aqueous solution followed by successive proton and alkali-ion exchange method. α-MnO2 with high surface area of 33–133.0m2 g−1 was successively synthesized and used as an electrode catalyst for Li–air battery. It was found that the mixture of Pd and mesoporous α-MnO2 electrode shows the high activity to oxidation and reduction of Li to form Li2O2 or Li2O. Application of Pd/mesoporous α-MnO2, which is mixed with teflonized acetylene binder (TAB), for air electrode is effective for decreasing the charge potential and also improved the energy efficiency as well as cyclability.