Based on mussel-inspired polydopamine (PDA), a novel technique to fabricate carbon nanowire (CNW) arrays is presented for a possible use of porous carbon electrode in electrochemical energy storage applications. PDA can give more porosity and nitrogen-doping effect to carbon electrodes, since it has high graphitic carbon yield characteristic and rich amine functionalities. Using such outstanding properties, the applicability of PDA for electrochemical energy storage devices was investigated. To achieve this, the decoration of the CNW arrays on carbon fiber surface was performed to increase the surface area for storage of electrical charge and the chemical active sites. Here, zinc oxide (ZnO) nanowire (NW) arrays were hydrothermally grown on the carbon fiber surface and then, PDA was coated on ZnO NWs. Finally, high temperature annealing was performed to carbonize PDA coating layers. For higher energy density, manganese oxide (MnOx) nanoparticles (NPs), were deposited on the carbonized PDA NW arrays. The enlarged surface area induced by carbon nanowire arrays led to a 4.7-fold enhancement in areal capacitance compared to that of bare carbon fibers. The capacitance of nanowire-decorated electrodes reached up to 105.7 mF/cm2, which is 59 times higher than that of pristine carbon fibers.