The nitrogen (N)-doped reduced graphene aerogel (NRGA) with high Ndoping level is successfully fabricated via chemical converted method and thermal activation. N-atoms can be incorporated at a high temperature of 900 °C and distort the lattice structure of RGA by the formation of different N-configuration bindings. NRGA exhibits a larger surface area than GA, and the surface morphology is roughened as characterized by microscopic analysis. As confirmed by X-ray photoelectron spectroscopy (XPS) result, the pyridinic- and/or pyrrolic-N bindings modified electronic structures to improve the electrochemical properties. The specific capacitance of NRGA is increased to 289 F g-1 at 10 mV s-1 with rate capability of 75% and cyclic stability of 86%. These excellent electrochemical performances of NRGA are due to the synergistic structure effect which provide a large accessible area and rapid ion transfer pathways, as well as N containing groups acting as the electrochemical active sites positioned at the edge or on-plane of NRGA lattices.