The development of new advanced nanostructures based on the hybridization of different carbon nanomaterials to obtain enhanced performance of energy storage devices has attracted considerable attention. Herein, a hierarchical nanostructure of carbon nanotubes supported electrospun carbon nanofiber networks (CNTs@CNFs) was successfully fabricated by using two facile techniques: - electrospinning and chemical vapor deposition (CVD). Such CNTs@CNFs hybrid showed the uniform and high density of CNTs directly grown on the surface of carbon nanofiber networks, leading to the formation of a hierarchical nanostructure with a large surface area and highly porous characteristics. The enhanced interactions between the CNTs and the CNFs networks were found to improve the electrical conductivity and electrochemical stability of the material. Owing to its unique nanoarchitectures and physicochemical properties, the CNTs@CNFs hybrid was demonstrated to be a potential electrode material for an electrochemical capacitor, in which a high specific capacitance of 464.2 F g(-1) at 0.5 A g(-1) and long-term stability with 97% retention after 10,000 repeated charge-discharge cycles were achieved. The obtained results suggest that the present CNTs@CNFs hybrid is a promising candidate for an electrochemical capacitor in energy storage technologies.