To achieve a high reversibility and long cycle life for lithium-oxygen (Li-O-2) batteries, the irreversible formation of Li2O2, inevitable side reactions, and poor charge transport at the cathode interfaces should be overcome. Here, we report a rational design of air cathode using a cobalt nitride (Co4N) functionalized carbon nanofiber (CNF) membrane as current collector-catalyst integrated air cathode. Brush-like Co4N nanorods are uniformly anchored on conductive electrospun CNF papers via hydrothermal growth of Co(OH)F nanorods followed by nitridation step. Co4N-decorated CNF (Co4N/CNF) cathode exhibited excellent electrochemical performance with outstanding stability for over 177 cycles in Li-O-2 cells. During cycling, metallic Co4N nanorods provide sufficient accessible reaction sites as well as facile electron transport pathway throughout the continuously networked CNF. Furthermore, thin oxide layer (<10 nm) formed on the surface of Co4N nanorods promote reversible formation/decomposition of film-type Li2O2, leading to significant reduction in overpotential gap (similar to 1.23 V at 700 mAh g(-3)). Moreover, pouch-type Li-air cells using Co4N/CNF cathode stably operated in real air atmosphere even under 180 degrees bending. The results demonstrate that the favorable formation/decomposition of reaction products and mediation of side reactions are hugely governed by the suitable surface chemistry and tailored structure of cathode materials, which are essential for real Li-air battery applications.