Microbial fuel cells (MFCs) can generate electricity from the oxidation of organic substrates using anodic exoelectrogenic bacteria and have great potential for harvesting electric energy from wastewater. Improving oxygen reduction reaction (ORR) performance at a neutral pH is needed for efficient energy production. Here we show a nitrogen doped (≈4 wt%) ionothermal carbon aerogel (NDC) with a high surface area, large pore volume, and hierarchical porosity, with good electrocatalytic properties for ORR in MFCs. The MFCs using NDC air cathodes achieved a high maximum power density of 2300 mW m−2, which was 1.7 times higher than the most commonly used Pt/C air cathodes and also higher than most state-of-the-art ORR catalyst air cathodes. Rotating disk electrode measurements verified the superior electrocatalytic activity of NDC with an efficient four-electron transfer pathway (n=3.9). These findings highlight NDC as a better-performing and cost-efficient catalyst compared with Pt/C, making it highly viable for MFC applications.