High cost and limited natural reserves of precious metals as oxygen reduction reduction (ORR) catalysts have hindered the practical application of microbial fuel cells (MFCs). Herein, the cost-effective catalysts were synthesized by co-doping binuclear-cobalt-phthalocyanine (Bi-CoPc) and cerium oxide (CeO2) on ordered mesoporous carbon (OMC). The catalysts Bi-CoPc/x%CeO2/OMC (x = 3, 6 and 12) with different CeO2 loading were physically characterized by Nitrogen physisorption, X-ray Diffraction, Transmission Electron Microscopy and X-ray Photoelectron Spectroscopy, and chemically characterized by Rotary Disk Electrode analysis. The relationship between the CeO2 content and ORR activity was investigated. The optimum CeO2 loading in the Bi-CoPc/6%CeO2/OMC catalyst provided the highest Ce3+ content that are favorable for the chemisorbed oxygen. Bi-CoPc/6%CeO2/OMC led to an increased half wave potential and limiting current density and to the further decreased over-potential. It also displayed a higher electron transfer number in comparison with Bi-CoPc/3%CeO2/OMC and Bi-CoPc/12%CeO2/OMC. The electrochemical results were closely related with the voltage generation obtained in single chamber MFC (SCMFCs) with air cathode. Bi-CoPc/6%CeO2/OMC-based SCMFC generated the highest power density of 486 +/- 6 mW/m(2) and achieved chemical oxygen demand removal of 79.3 +/- 1.5%. The voltage generation for Bi-CoPc/6%CeO2/OMC decreased only by 3.7% after 1300 h of operation, indicating its good stability in MFCs large scale application. (C) 2019 The Electrochemical Society.