Stable perovskite oxide is considered as a potential cathode for microbial fuel cells (MFCs). Herein, Zn is used as an effective element to modify the micro-structure and oxygen vacancy of perovskite to be a novel cathode catalyst. Physical characterizations show that due to partial volatilization at high temperature of Zn, perovskite forms hierarchically porous structures. Moreover, Zn is precipitated in electrochemical reaction to generate Zn vacancy in situ; thus, the active center of Fe has a superior interaction with oxygen-containing species, promoting the production of oxygen vacancy and forms a mixed valence state of Fe2+/Fe3+. The Zn-doped perovskite material CaFe0.7Zn0.3O3 exhibits remarkable oxygen reduction reaction (ORR) performances with outstanding onset potential (0.194 V vs. Ag/AgCl) and half-wave potential (-0.219 V vs. Ag/AgCl) under alkaline condition, which is better than Pt/C catalyst. Besides, CaFe0.7Zn0.3O3 shows an excellent four-electron pathway of ORR mechanism with remarkable corrosion resistance and stability, which enables a more reliable cathode electrocatalyst. The maximum power density of CaFe0.7Zn0.3O3 (892.10 +/- 90.79 mW m(-3)) testing on microbial fuel cell is comparable to the maximum power density (1012.86 +/- 84.03 mW m(-3)) of Pt/C. The findings of this work provide the feasibility of exploring inexpensive and high-performance cathode catalyst.