The high performance of α–MnO2/NGNF catalyzed air cathode for Li–O2 battery is reported in this article. The α–MnO2 nanorods are successfully grown on highly conductive nitrogen doped graphite nanofibers with caterpillar like morphology by a simple hydrothermal technique. The as–prepared α–MnO2/N–GNF catalyst exhibits better electrocatalytic performance in terms of oxygen reduction and evolution reactions in the air cathode exhibiting comparatively low overpotential. In addition to the low overpotential, α–MnO2/NGNF catalyzed Li–O2 battery also show high capacity, reversibility and rate capability. The combined effect of α–MnO2 and N–GNF for facilitating electrochemical reactions between Li and O2 is described for improving energy and columbic efficiency of Li–O2 battery.