A simple method for synthesizing highly active electrocatalyst with bimetal Cu/Co and N co-doped porous carbon structures framework is reported in this study. The addition of Cu and Co elements improve the chemical and physical properties of the electrocatalyst, including abundant valid active sites, large specific surface area and good conductivity, which significantly boost electrocatalytic performances in oxygen reduction reaction (ORR). The onset and half-wave potentials of catalyst (Cu/Co/N-C#2) are 0.25 and 0.14 V (vs Ag/AgCl), respectively, which are positive than those of the 20% Pt/C catalysts. Moreover, the maximum output voltage and power density of the Cu/Co/N-C#2 catalyst-based air cathode microbial fuel cells (MFCs) are enhanced to 677 mV and 1008 mW m(-2), respectively, which are 1.25 and 1.31 times higher than those of the 20% Pt/C catalyst-based MFCs. This strategy using Cu-doped ZIF-67 as precursor to prepare bimetal- and nitrogen-codoped hollow carbon structures is a feasible method to boost ORR catalytic performance. (C) 2019 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.