A three-dimensional (3D) Ni-MOF of the formula [Ni(C4H4N2)(CHO2)2]n, has been reported, which shows a capacitance of 2150 F/g at a current density of 1A/g in a three-electrode setup (5.0 M KOH). Post-mortem analysis of the sample after three-electrode measurements revealed the bias-induced transformation of Ni-MOF to Ni(OH)2, which has organic constituents intercalated within the sample exhibiting better storage performance than bulk Ni(OH)2. Afterward, the synthesized MOF and reduced graphene (rGO) were used as the anode and cathode electrode material, respectively, and a two-electrode asymmetric supercapacitor device (ASC) setup was designed that exhibited a capacitance of 125 F/g (at 0.2 A/g) with a high energy density of 50.17 Wh/kg at a power density of 335.1 W/kg. The ASC further has a very high reversibility (97.9% Coulombic efficiency) and cyclic stability (94%) after 5000 constant charge-discharge cycles. Its applicability was also demonstrated by running a digital watch. Using sophisticated density functional theory simulations, the electronic properties, diffusion energy barrier for the electrolytic ions (K+), and quantum capacitance for the Ni(OH)2 electrode have been reported. The lower diffusion energy barrier (0.275 eV) and higher quantum capacitance (1150 μF/cm2) are attributed to the higher charge storage performance of the Ni-MOF-transformed Ni(OH)2 electrode as observed in the experiment.