Cost-effective atomically dispersed Fe-N-P-C complex catalysts are promising to catalyze the oxygen reduction reaction(ORR)and replace Pt catalysts in fuel cells and metal-air batteries.However,it remains a challenge to increase the number of atomically dispersed active sites on these catalysts.Here we report a highly efficient impregnation-pyrolysis method to prepare effective ORR electrocatalysts with large amount of atomically dispersed Fe active sites from biomass.Two types of active catalyst centers were identified,namely atomically dispersed Fe sites and FexP particles.The ORR rate of the atomically dis-persed Fe sites is three orders of magnitude higher than it of FexP particles.A linear correlation between the amount of the atomically dispersed Fe and the ORR activity was obtained,revealing the major con-tribution of the atomically dispersed Fe to the ORR activity.The number of atomically dispersed Fe increases as the Fe loading increased and reaching the maximum at 1.86 wt％Fe,resulting in the maxi-mum ORR rate.Optimized Fe-N-P-C complex catalyst was used as the cathode catalyst in a homemade Zn-air battery and good performance of an energy density of 771 Wh kgZn-1,a power density of 92.9 mW cm-2 at 137 mA cm-2 and an excellent durability were exhibited.