Using simple microwave irradiation under the presence of sodium amide as a nitrogen source, preparation of nitrogen-doped graphene nanosheets has been successfully demonstrated. It is notable that exfoliation and nitrogen doping of graphite to nitrogen-doped graphene simultaneously occurred during the microwave irradiation within a minute, and nitrogen content of the doped graphene could reach up to 8.1%. It was also found that the binding configuration of nitrogen atom on graphitic layer consisted of various nitrogen-containing moieties such as pyridine-N, pyrrolic-N, and quaternary-N, and their composition was changed as a function of irradiation power. Although formation of undoped reduced graphene oxide by microwave irradiation resulted in slight increase of electrical conductivity because of the reductive recovery of oxidized graphite to graphene, nitrogen doping involved during irradiation induced much more notable increase of electrical conductivity more than 300 S cm(-1). Furthermore, nitrogen-doped graphene showed highly enhanced capacitive performance than that of undoped reduced graphene oxide, the specific capacitance of 200 F/g (current density of 0.5 A/g), which ascribes the pseudocapacitive effect from the incorporation of nitrogen atom on graphitic layer.