Densely-packed nanorods (NRs) of highly-crystalline hexagonal WO₃ (h-WO₃) are grown on carbon cloth substrate using a hydrothermal method. XRD data reveal that the structure comprises an open framework of interconnected WO₆ octahedra with numerous cavities running across the NR length. These tunnels facilitate fast intercalation/deintercalation of protons during electrochemical reactions in conjunction with the surface-based redox processes, thereby contributing significantly towards high-charge storage capacity of WO₃ anode. On the positive electrode, these NRs have been utilized as scaffold to deposit nano-flakes of MnO₂, thus forming WO₃/MnO₂ core/shell NRs. The cathode shows attractive capacitance value of 2361 mF/cm² which is higher than the value for pristine MnO₂ nano-flakes at a current density of 1 mA/cm² and is facilitated by the high surface area owing to the core-shell NR design together with mixed protonic-electronic conductivity of WO₃ NRs. The assembled WO₃//WO₃/MnO₂ hybrid asymmetric supercapacitor exhibits volumetric capacitance of 7.22 F/cm³ together with maximum energy and power density values of 3.25 mWh/cm³ and 411 mW/cm³, respectively, within a potential window of 1.8 V. Accordingly, the study demonstrates the versatility of h-WO₃ in designing both the negative and positive electrodes for hybrid ultracapacitors.