Biofilm-coated electrodes and outer cell membrane-mimicked electrodes were examined to verify an extracellular electron transfer mechanism using Marcus theory for a donor-acceptor electron transfer. Redox couple-bound membrane electrodes were prepared by impregnating redox coenzymes into Nafion films on carbon cloth electrodes. The electron transfer was believed to occur sequentially from acetate to nicotinamide adenine dinucleotide (NAD), c-type cytochrome, flavin mononucleotide (FMN) (or riboflavin (RBF)) and the anode substrate. Excellent polarisation and power density characteristics were contributed by the modification of the cathode with a high-surface-area ordered mesoporous carbon or a hollow core-mesoporous shell carbon. The maximum power density of the microbial fuel cell (MFC) could be improved by a factor of two mainly due to the accelerated electron consumption by modifying the cathode surfaces within three-dimensionally interconnected mesoporous carbon particles, and the anode was coated with a mixed culture of anaerobic bacteria.