In this work, g-C3N4@GO gel-like hybrid is obtained by assembling intentionally exfoliated g-C3N4 sheets on graphene oxide (GO) sheets under a hydrothermal condition. A specific N-doping process is first designed by heating the g-C3N4@GO interlaced hybrid in vacuum to form nitrogen-doped graphene nanosheets (NGS) with high level of pyridinic-N (56.0%) and edge-rich defect structure. The prepared NGS exhibited a great electrocatalysis for oxygen reduction reaction (ORR) in terms of the activity, durability, methanol tolerance, and the reaction kinetics. And the excellent electrocatalytic performance stems from the effective N-doped sites that the nitrogen atom is successfully doped at the defective edges of graphene, and the annealing temperature can play significant role of the doping pattern and location of N. The research provides a new insight into the enhancement of electrocatalysis for ORR based on nonmetal carbons by using the novel N-doping method.