Abstract We report a facile, low‐cost approach to fabricate N, B‐codoped graphene aerogel/PPy composites for an asymmetric supercapacitor. The supercapacitor is based on the traditional sandwich‐like structure composed of NBGA@PPy‐TB as anode material and PPy‐TB as cathode material. Analysis of NBGA@PPy‐TB microstructure reveals that the PPy‐TB is successfully coated onto the NBGA. The 3D cross‐linked networking structures and heteroatom composition endow the NBGA@PPy‐TB electrode with high specific capacity (566 F/g at 1 A/g). The electrochemical properties of asymmetric all‐solid supercapacitor, such as capacitance, impedance, cycling stability, are discussed. The supercapacitor exhibits a fair specific capacity (160.3 F/g at 0.5 A/g).