The bundled Fe2O3 nanorods are vertically grown on hollow carbon fibers (aCF). Needle-like nickel-cobalt double hydroxide (NiCo-DH) grown on aCF displays hierarchical porous network. Both aCF-Fe2O3 anode and aCF-NiCo-DH cathode exhibit very high specific capacitance with good rate capability. An asymmetric capacitor build with aCF-Fe2O3 and aCF-NiCo-DH as electrode delivers an energy density of 83.7 Wh kg−1 with remarkable cycling stability.