Rational design of low-cost, highly electrocatalytic activity, and stable bifunctional electrocatalysts for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) has been a great significant for metal–air batteries. Herein, an efficient bifunctional electrocatalyst based on hollow cobalt oxide nanoparticles embedded in nitrogen-doped carbon nanosheets (Co/N-Pg) is fabricated for Zn–air batteries. A low-cost biomass peach gum, consisting of carbon, oxygen, and hydrogen without other heteroatoms, was used as carbon source to form carbon matrix hosting hollow cobalt oxide nanoparticles. Meanwhile, the melamine was applied as nitrogen source and template precursor, which can convert to carbon-based template graphitic carbon nitride by polycondensation process. Owing to the unique structure and synergistic effect between hollow cobalt oxide nanoparticles and Co-N-C species, the proposal Co/N-Pg catalyst displays not only prominent bifunctional electrocatalytic activities for ORR and OER, but also excellent durability. Remarkably, the assembled Zn–air battery with Co/N-Pg air electrode exhibited a low discharge-charge voltage gap (0.81 V at 50 mA cm–2) and high peak power density (119 mW cm–2) with long-term cycling stability. This work presents an effective approach for engineering transition metal oxides and nitrogen modified carbon nanosheets to boost the performance of bifunctional electrocatalysts for Zn–air battery.