Carbon nanofibers (CNFs)/MnO2 nanocomposites were prepared as freestanding electrodes using in situ redox deposition and electrospinning. The electrospun CNFs substrates with porosity and interconnectivity enabled the uniform incorporation of birnessite-type MnO2 deposits on each fiber, thus showing unique and conformal coaxial nanostructure. CNFs not only provided considerable specific surface area for high mass loading of MnO2 but also offered reliable electrical conductivity to ensure the full utilization of MnO2 coatings. The effect of MnO2 loading on the electrochemical performances was investigated by cyclic voltammetry (CV), impedance measurements and Galvonostatic charging/discharging technique. The results showed that an ultrathin MnO2 deposits were indispensable to achieve better electrochemical performance. The maximum specific capacitance (based on pristine MnO2) attained to 557F/g at a current density of 1A/g in 0.1M Na2SO4 electrolyte when the mass loading reached 0.33mg/cm2. This freestanding electrode also exhibited good rate capability (power density of 13.5kW/kg and energy density of 20.9Wh/kg at 30A/g) and long-term cycling stability (retaining 94% of its initial capacitance after 1500 cycles). These characteristics suggested that such freestanding CNFs/MnO2 nanocomposites are promising for high-performance supercapacitors.