We report on a novel biocompatible, highly conductive three-dimensional cathode manufactured by direct growth of flexible multiwalled carbon nanotubes on reticulated vitreous carbon (NanoWeb-RVC) for the improvement of microbial bioelectrosynthesis (MES). NanoWeb-RVC allows for an enhanced bacterial attachment and biofilm development within its hierarchical porous structure. 1.7 and 2.6 fold higher current density and acetate bioproduction rate normalized to total surface area were reached on NanoWeb-RVC versus a carbon plate control for the microbial reduction of carbon dioxide by mixed cultures. This is the first study showing better intrinsic efficiency as biocathode material of a three-dimensional electrode versus a flat electrode: this comparison has been made considering the total surface area of the porous electrode, and not just the projected surface area. Therefore, the improved performance is attributed to the nanostructure of the electrode and not to an increase in surface area. Unmodified reticulated vitreous carbon electrodes lacking the nanostructure were found unsuitable for MES, with no biofilm development and no acetate production detected. The high surface area to volume ratio of the macroporous RVC maximizes the available biofilm area while ensuring effective mass transfer to and from the biofilm. The nanostructure enhances the bacteria-electrode interaction and microbial extracellular electron transfer. When normalized to projected surface area, current densities and acetate production rates of 3.7 mA cm⁻² and 1.3 mM cm⁻² d⁻¹, respectively, were reached, making the NanoWeb-RVC an extremely efficient material from an engineering perspective as well. These values are the highest reported for any MES system to date.