Microbial fuel cells (MFCs) are promising devices that convert chemical energy into electrical energy via extracellular electron transfer between bacteria and electrodes. However, inefficient extracellular electron transfers and bacteria/electrode interactions often limit their performance. Herein, we demonstrate a hybrid hydrogel assembled by a 2D covalent organic framework (COF) and reduced graphene oxide (rGO) nanosheets as anode materials for MFCs. The 2D COF nanosheets effectively prevent the stacking of rGO nanosheets, resulting in the hybrid hydrogel with a high specific surface area (313.2 m2/g), abundant mesopores and macropores, and high electrical conductivity (492 S/m). The COF material also brings many quinone groups as redox mediators to facilitate electron transfer between bacteria and electrodes. The COF/rGO hybrid hydrogel enhances the growth of Shewanella decolorationis S12 cells, even under the influence of different organic dyes. Dense biofilms are formed on the hybrid hydrogel's surface and inside its macropores, further improving extracellular electron transfers. Assembled MFCs using COF/rGO anodes deliver a maximum power density of 905.1 mW/m2 and can operate for 600 h. They also enable simultaneous power generation and fast organic contamination degradation in electrolytes. This work shows the potential of using 2D nanoarchitectures to promote high-performance MFCs.