This paper presents highly conductive carbon nanofiber/MnO2 coaxial cables in which individual electrospun carbon nanofibers are coated with an ultrathin hierarchical MnO2 layer. In the hierarchical MnO2 structure, an around 4 nm thick sheath surrounds the carbon nanofiber (CNF) in a diameter of 200 nm, and nano-whiskers grow radically outward from the sheath in view of the cross-section of the coaxial cables, giving a high specific surface area of MnO2. The CNFs are synthesized by electrospinning a precursor containing iron acetylacetonate (AAI). The addition of AAI not only enlarges the specific surface area of the CNF but also greatly enhances their electronic conductivity, which leads to a dramatic improvement in the specific capacitance and the rate capability of the CNF/MnO2 electrode. The AAI-CNF/MnO2 electrode shows a specific capacitance of 311 Fg(-1) for the whole electrode and 900 Fg(-1) for the MnO2 shell at a scan rate of 2 mV s(-1). Good cycling stability, high energy density (80.2 Wh kg(-1)) and high power density (57.7 kW kg(-1)) are achieved. This work indicates that high electronic conductivity of the electrode material is crucial to achieving high power and energy density for pseudo-supercapacitors. (C) 2012 Elsevier B.V. All rights reserved.