Electrocatalysts for catalyzing oxygen reduction reactions at variable pH conditions are essential for energy conversion and storage. Herein, Fe@FeCoZn–CN electrocatalysts were prepared with internal and external doping approach. The Fe@FeCoZn–CN electrocatalyst exhibits a desirable ORR performance in both acid and alkaline electrolytes. Specifically, the half-wave potential (E1/2) of Fe@FeCoZn–CN electrocatalyst is 0.890 V which far beyond Pt/C electrocatalyst (0.839 V) in alkaline electrolyte. In addition, Fe@FeCoZn–CN electrocatalyst also exhibits improved ORR activity (E1/2 = 0.801 V) compared to Pt/C (0.797 V) electrocatalysts in acidic electrolytes. What's exciting is that the rechargeable ZABs based on Fe@FeCoZn–CN electrocatalysts exhibit an impressive performance with a favorable open-circuit potential of 1.517 V and a promising specific capacity is 833.7 mA h gzn−1, good charge/discharge cycle stability. The remarkable ORR catalytic performance of Fe@FeCoZn–CN electrocatalysts can be traced to the internal doping of metals which prevent excessive metal aggregation and surface modified which can increase the metal loading to expose more active sites.