Zinc-air batteries (ZABs), as a new type of energy storage and conversion device, have received lots of attention due to their high energy density and low cost. The electrode material is a key factor for improving the performance of ZABs. Here, a facile strategy for the fabrication of N-rich porous carbon is reported. H3BTC and GO are selected as carbon precursors, histidine and Fe(NO3)3 are used as ligands, and urea is used as a N source and template. After the conventional drying of the complex and following carbonization process, serial N-doped carbon materials are prepared. The composition and structure of the material are characterized, and the effect of the ligand is studied. The hierarchical porous structure facilitates the full exposition of N and trace of Fe active sites and benefits the transportation of electrolytes, thus improving the oxygen reduction reaction (ORR). The ORR performances show that the porous carbon has a positive initial and half-wave potential, good limiting current density, a near four-electron transfer process, and better methanol resistance and durability. The assembled ZAB exhibits high specific capacity (880.4 mAh gZn-1), excellent open-circuit voltage (1.54 V), and superior cycling stability, which further provides the significant potential for its application.