Template-directed N-doped mesoporous graphene (NMG) is obtained by the chemical vapor deposition methodology in a fluidized bed reactor using C2H4 and NH3 as carbon source and dopant, respectively. The in situ N incorporation into the carbon framework can be achieved along with the growth of graphene, guaranteeing the uniformity of N doping. In the Li-based half-cell systems, NMG electrode exhibits outstanding electrochemical behaviors in view of the cathode and anode, respectively, which is superior to those of the corresponding activated carbon cathode and undoped MG anode. Benefiting from the tremendous mesoporous channels and N doping, the lithium-ion capacitor configured with NMG as cathode and anode presents superior capacitive energy-storage behaviors with respect to the capacitance, energy density, power density and durability. This work provides a good strategy of the combination of structure control and N doping to obtain the high-performance electrode material for capacitive energy-storage devices.