Cathode electrocatalyst is quite critical to realize the application of microbial fuel cells (MFCs). Perovskite oxides have been considered as potential MFCs cathode catalysts to replace Pt/C. Herein, Cu-doped perovskite oxide with a stable porous structure and excellent conductivity was successfully prepared through a sol-gel method. Due to the incorporation of Cu, CaFe0.9Cu0.1O3 has more micropores and a larger surface area, which are more conducive to contact with oxygen. Doping Cu resulted in more Fe3+ in B-site and thus enhanced its binding capability to oxygen molecules. The data from electrochemical test demonstrated that the as-prepared catalyst has good conductivity, high stability, and excellent ORR properties. Compared with Pt/C catalyst, CaFe0.9Cu0.1O3 exhibits a lower overpotential, which had an onset potential of 0.195 V and a half-wave potential of 0.224 V, respectively. CaFe0.9Cu0.1O3 displays an outstanding four-electron pathway for ORR mechanism and demonstrates superiors corrosion resistance and stability. The MFC with CaFe0.9Cu0.1O3 has a greater maximum power density (1090 mW m(-3)) rather than that of Pt/C cathode (970 mW m(-3)). This work demonstrated CaFe0.9Cu0.1O3 is an economic and efficient cathodic catalyst for MFCs.