The binder-free flexible carbon paper (FCP) supported mutil-wall carbon nanotubes (CNTs) were synthesized via CVD method. Subsequently, polyaniline was deposited on the surface of CNTs/FCP, which was followed by polyaniline carbonization and KOH activation to obtain nitrogen-doped (N-doped) carbon/CNTs/FCP composite. The Raman spectroscopy, scanning electron microscope, transmission electron microscope investigation indicated that N-doped carbon/ CNTs/FCP was formed after the polyaniline carbonization and KOH activation, without destroying the intrinsic CNTs structure. Compared to the pristine CNTs/FCP, of which the specific capacitance(Csp) was 5.23 F/g and 8.24 F/g in 1M H2SO4 and 0.5M KOH solution respectively, the reversible Csp of N-doped carbon/CNTs/FCP reached 193.3 F/g (1M H2SO4) and 161.0 F/g (0.5M KOH), at the current density of 1 A/g. Moreover, this 3D structure N-doped carbon/CNTs/FCP shows good hydrophility and excellent cycling performance with little capacitance loss over long term galvanostatic charge-discharge, which is a promising electrode material for supercapacitor application.