The present study reports about the fabrication of a three-dimensional (3D) macroporous steel-based scaffold as an anode to promote specifically bacterial attachment and extracellular electron transfer to achieve power density as high as 1184 mW m–2, which is far greater than that of commonly used 3D anode materials. The unique 3D open macroporous configuration of the anode and the microstructure generated by the composite coating provide voids for the 3D bacterial colonization of electroactive biofilms. This is attributed to the sizeable interfacial area per unit volume provided by the 3D corrugated electrode that enhanced the electrochemical reaction rate compared to that of the flat electrode, which favors the enhanced mass transfer and substrate diffusion at the electrode/electrolyte interface and thereby increases the charge transfer by reducing the electrode overpotential or interfacial resistance. In addition, bacterial infiltration into the interior of the anode renders large reaction sites for substrate oxidation without the concern of clogging and biofouling and thereby improves direct electron transfer. A very low overpotential (−27 mV) with a very low internal resistance (7.104 Ω cm2) is achieved with the fabricated microbial fuel cell (MFC) that has a modified 3D corrugated electrode. Thus, easier and faster charge transfer at the electrode–electrolyte interface is confirmed. The study presents a revolutionary practical approach in the development of highly efficient anode materials that can ensure easy scale-up for MFC applications.