Hydrothermally obtained MoO₃/reduced graphene oxide (RGO) hybrid registered a specific capacitance of 724 F g^‑1 at 1 A g^‑1, superior to the supercapacitor performance obtained from similar hybrid structures. Density functional theory (DFT) simulations further corroborated our claim in terms of both enhanced quantum capacitance and relevant insight from the electronic density of states (DOS) for MoO₃/RGO. Maximum capacitance is achieved for 12 wt % of RGO and then it reduces as observed in the experiment. The appearance of additional density of states from the C p_z orbital in the band gap region near the Fermi level on introduction of RGO in MoO₃ is responsible for the enhanced capacitance in MoO₃/RGO.