Transition metal phosphides (TMPs) with high electrocatalytic activity for the oxygen evolution reaction (OER) are reckoned as a substitution of precious group metals catalysts in rechargeable Zn-air battery. In this work, Co/Co2P heterojunction nanoparticles supported N,P-doped carbon nanosheets (Co/Co2P@NPCNS) were designed and prepared via a facile one-step molten salt-assisted pyrolysis process. Density function theory calculations reveal that the heterogeneous interactions of Co/Co2P effectively enhance the bifunctional electrocatalytic activity for oxygen reduction reaction (ORR) and OER. The synergistic interaction between the Co/Co2P heterojunction nanoparticles with highly exposed active sites and excellent catalytic activity and the two-dimensional doped carbon nanosheets with high conductivity contributes to Co/Co2P@NPCNS exhibiting preeminent bifunctional ORR/OER activity and stability with a high half-wave potential for ORR (0.87 V), a low overpotential for OER (302 mV at 10 mA cm−2) and a low potential gap (0.66 V). The homemade rechargeable Zn-air battery performs high peak power density (187 mW cm−2) and exceptional endurance. This heterogeneous interface tactic of integrating TMPs with heteroatom-doped carbon materials may shed light on the research and development of non-precious metal electrocatalysts.