Microbial fuel cells (MFCs) are a promising clean energy source to directly convert waste chemicals to available electric power. However, the practical application of MFCs needs the increased power density, enhanced energy conversion efficiency and reduced electrode material cost. In this study, three-dimensional (3D) macroporous N, P and S co-doped carbon foams (NPS-CFs) were prepared by direct pyrolysis of the commercial bread and employed as free-standing anodes in MFCs. As-obtained NPS-CFs have a large specific surface area (295.07 m2 g−1), high N, P and S doping level, and excellent electrical conductivity. A maximum areal power density of 3134 mW m−2 and current density of 7.56 A m−2 are generated by the MFCs equipped with as-obtained NPS-CF anodes, which is 2.57- and 2.63-fold that of the plain carbon cloth anodes (areal power density of 1218 mW m−2 and current density of 2.87 A m−2), respectively. Such improvement is explored to mainly originate from two respects: the good biocompatibility of NPS-CFs favors the bacterial adhesion and enrichment of electroactive Geobacter species on the electrode surface, while the high conductivity and improved bacteria-electrode interaction efficiently promote the extracellular electron transfer (EET) between the bacteria and the anode. This study provides a low-cost and sustainable way to fabricate high power MFCs for practical applications.