Highly efficient and stable bifunctional electrocatalysts for ORR and OER are essential for fabricating rechargeable zinc–air batteries. Herein, we prepared metal-free N,P-codoped hydrophilic carbon nanosheets (NPC-“Li”) as effective bifunctional electrocatalysts using LiCl as the medium, in which phytic acid was used as the source of phosphorous and carbon, and ammonia atmosphere as the source of nitrogen. Furthermore, micrometer-sized agglomerations of carbon materials were significantly restrained using LiCl. NPC-“Li” exhibits superior bifunctional catalytic activity for both ORR and OER. In addition, the NPC-“Li”-based primary zinc–air battery shows a high energy density of 908 Wh kg_Zn⁻¹, and the rechargeable battery shows excellent charge–discharge cycle efficiency.