The broad application of metal-air batteries and fuel cells have been greatly limited due to their slow kinetics of oxygen electrodes involving the oxygen reduction reaction (ORR), and therefore the development of high-efficient, low-cost and high-reserve ORR electrocatalysts is of great significance. Herein, a hypersaline-protected pyrolysis strategy is presented for preparing 3D honeycombed cobalt, nitrogen co-doped carbon nanosheets (Co/N-CNS) by using eco-friendly biomass as a carbon and nitrogen source. During the hypersaline-protected pyrolysis, the pyridinic nitrogen-rich biomass facilitates the formation of highly active Co/N active sites among the resultant Co/N-CNS, while the templating-washing-drying cyclic utilization of salts creates honeycombed pore structures among the Co/N-CNS. Due to the structural features of honeycombed pores and uniform distributed active sites, the Co/N-CNS catalyst offers excellent ORR activity, high durability and methanol-tolerant performance in an alkaline electrolyte. As a demonstration, a primary Zn-air battery using the Co/N-CNS cathode delivers a high power density and excellent operating stability beyond that of commercial Pt/C cathode.