Utilization of bifunctional high-efficiency non-precious electrocatalysts for stable and effective water splitting is crucial to the growth of the clean energy industry. Topologically, the predetermined ordered structures of metal-organic frameworks (MOFs) can be contrived through the judicious assembly of a tailor-made synthesis strategy of layered double hydroxide (LDH) films. Aiming at NiCo-LDH@NH2-UiO-66 as a model system, for the first time, we examine the 2-methyl imidazole-induced ultrathin 2D NiCo-LDH nanosheet arrays in NH2-UiO-66 as an effective bifunctional electrocatalytic system for overall H2O splitting with marvellous performance and robustness in alkaline environments. The progressively tuned NiCo-LDH@NH2-UiO-66 catalyst demands overpotential values of 296 and 224 mV to deliver a current density of 50 mA cm−2 for the O2 evolution reaction (OER) and H2 evolution reaction (HER) in 1 M KOH aqueous solution, respectively. Tafel studies also revealed favorable reaction kinetics during electrochemical processes. The NiCo-LDH@NH2-UiO-66 bifunctional electrode displayed superior activity exhibiting a voltage of 1.65 V at a benchmarking current density of 10 mA cm−2 towards overall water splitting. Importantly, the NiCo-LDH@NH2-UiO-66 electrode shows an excellent specific capacitance of 0.00364 mF cm−2 with remarkable durability of the capacitor after 1000 cycles. To compare with the experimental result, we have performed density functional theory (DFT)-based calculation to estimate the HER and OER activity of the NiCo-LDH@NH2-UiO-66 heterostructure. From the HER free energy profile and Bader charge analysis, we have confirmed that the presence of NH2-UiO-66 helps in H2 production with 0.10 eV free energy of H2 adsorption (GH*). From the OER free energy profile, the estimated overpotential (η) is about 0.96 eV, which confirms that the electrochemical reaction towards the OER is also possible on the NiCo-LDH@NH2-UiO-66 structure. This study will bestow a beneficial blueprint for the utilization of an effective, durable, and economical MOF-based bifunctional catalytic system for overall water splitting.