A bifunctional air cathode for the electrochemical oxygen reduction and evolution in a Li-O2 battery comprising Co-CoO nanoparticles embedded in the nitrogen-doped carbon nanorods (Co-CoO/N-CNR) is presented. The nanorod morphology with mesoporous nanostructures can handle continuous formation and decomposition of Li2O2 and favors the transport of electrons and ions, therefore improves the rate capability and cycle stability. Moreover, the hierarchical mesoporous Co-CoO/N-CNR reduces the overall overpotential over the cycle and decreases the side reaction between Li2O2 and carbon surface, leading to a significant enhancement of the specific capacity and cycling capability. With the cooperative effect of Co-CoO/N-CNR and porous nature, Co-CoO/N-CNR cathode delivers a high discharge specific capacity of 10,555 mAh g−1 at 100 mA g−1 and long cycle stability for over 86 cycles without any capacity loss at a high cutoff capacity of 1000 mAh g−1. Furthermore, excellent performance of 7514 mAh g−1 at 500 mA g−1 is achieved.