Nitrogen-doped graphene-based aerogels with three levels of hierarchically organized pores were prepared via a simple environmentally friendly process, and successfully tested in supercapacitor applications. Mesopores and macropores were formed during the aerogel preparation followed by carbonization and its chemical activation by potassium hydroxide (KOH). These mesopores and macropores consist of amorphous carbon and a 3D graphene framework. Thermal treatment at 700 °C, 800 °C, 900 °C in N2 atmosphere was done to etch out the amorphous carbon and obtain a stable N-doped 3D graphene. Specific capacitance values obtained from the electrochemical measurements are in the range of 232–170 F× g−1. The thus fabricated structures showed excellent cyclic stability, suggesting that these materials have potential as electrodes for solid asymmetric supercapacitors.