The high ratio of pyridinic and pyridone N-doped graphene sheets have been synthesized by functionalizing graphene oxide (GO) with different oxygen groups on its surface. The typical N-doped graphene was determined to be ~3-5 layers by transmission electron microscopy (TEM) and atomic force microscopy (AFM), and the nitrogen content was measured as 6.8-8 at. % by X-ray photoelectron spectroscopy (XPS). The structure of the N-doped graphene with different surface functional groups was characterized by Raman spectroscopy. The research result indicates that the carboxylation of GO is the key factor to obtain pyridinic and pyridone N types during the N atom doping process. Compared to general N-doped graphene, the electrochemical test shows that specific capacitance of the GO-OOH-N sample reaches up to 217 F/g at a discharge current density 1 A/g and stable cycling performance (keep 88.8 % specific capacitance after 500 cycles at the same discharge current density) when applied to the supercapacitor electrode materials.