Enhanced simultaneous decolorization of Congo red and bioelectricity generation with anthraquinone-2,6-disulphonic disodium salt (AQDS), riboflavin (RF) and humic acid (HA) as mediators in air-cathode microbial fuel cell (MFC) was demonstrated. Compared with mediator-free MFC, the MFC with added 0.005 mM AQDS, 0.005 mM RF or 1 g/L HA showed 36%, 26% and 15% increase in maximum power density along with 394%, 450%, and 258% increases in decolorization rates of Congo red, respectively. Addition of mediators at higher concentration further increased power and Congo red decolorization but the increases were not proportional to the rise in mediator concentration. Based on decreases of anode charge transfer resistance and increases of Congo red decolorization, the mediators kinetically promote the extracellular electron transfer between bacteria, anode and Congo red. Microbial analysis showed that addition of mediators changed the composition of anodic microbial community and stimulated the growth of species belonging to Chlorobi, Endomicrobia and Firmicutes. (C) 2013 Elsevier Ltd. All rights reserved.