A hierarchical high-performance electrode with nanoacanthine-style polyaniline (PANI) deposited onto a carbon nanofiber/graphene oxide (CNF/GO) template was successfully prepared via an in situ polymerization process. The morphology analysis shows that introducing one-dimensional (1D) CNF could significantly decrease/inhibit the staking of laminated GO to form an open-porous CNF/GO architecture. Followed with in situ facial deposition of PANI, the as-synthesized PANI modified CNF/GO exhibits three-dimensional (3D) hierarchical layered nanoarchitecture, which favors the diffusion of the electrolyte ions into the inner region of active materials. The hierarchical free-standing electrodes were directly fabricated into sandwich structured supercapacitors using 1 M H2SO4 as the electrolyte showing a significant specific capacitance of 450.2 F/g at the voltage scan rate of 10 mV/s. The electrochemical properties of the hierarchical structure can be further improved by a reduction procedure of GO before the deposition of PANI.