• Graphene- wrapped MOF-derived bimetallic bifunctional electrocatalyst was developed. • The unique porous structure favorable for active sites exposure is obtained. • Transition of NiCo@rGO catalyst during the reaction is probed by in-situ Raman spectra. • NiCo@rGO delivers good ORR/OER activity and stability performance in Zn-air Battery. Developing efficient and cyclically stable bifunctional electrocatalysts towards oxygen evolution/reduction reactions (OER/ORR) is both critical and challenging for the application of zinc-air batteries (ZABs). In this work, a reduced graphene oxide-encapsulated, metal-organic framework (MOF) derived NiCo bimetallic nanoparticles embedded carbon-based bifunctional catalyst (NiCo@rGO) was successfully prepared. The intertwining of flaky rGO and MOF derivatives results in a large specific surface area and abundant pore structure, which is favorable for exposure of active catalytic sites and mass transfer, ensuring high electronic conductivity at the same time. The cooperation of cobalt and nickel nanoparticles enriches the active centers and increases the intrinsic catalytic activity compared with monometallic Co nanoparticles, leading to enhanced catalytic performance. Benefiting from the above advantages, NiCo@rGO exhibits efficient catalytic activities with an oxygen reduction half-wave potential of 0.85 V and oxygen evolution overpotential of 470 mV at 10 mA cm -2 . Furthermore, the ZABs with NiCo@rGO exhibits a superior open-circuit voltage of 1.49 V, a peak power density of as high as 110.45 mW cm -2 and excellent stability over 180 h. This contribution paves a practical avenue to construct bimetal-rGO composites for high-performance ZABs.