Electrochemically anodic exfoliation of graphite has been developed for nitrogen-doped few-layer graphene sheets (N-FLGS), demonstrating high N-doping levels of 6.05 atom%. The process for the preparation of N-FLGS is involved with the intercalation of glycine anions H2NCH2COO− into the graphite layers, electro-polymerization of large electro-oxidation products H2NCH2CONHCH2 −, and in situ N-doping in the graphite layer. Transmission electron microscopy, X-ray photoelectron spectroscopy, X-ray diffraction, and Raman spectroscopy were employed to characterize the structure and properties of the N-FLGS. The as-fabricated N-FLGS utilized as electrode materials for supercapacitor exhibit enhanced electrochemical performance, including excellent cycling stability (the capacitance ratios after 10 000 cycles is 96.1%) and a remarkable rate capability (184.5Fg−1 at 1Ag−1, 132.7Fg−1 at 50Ag−1).