In recent years, supercapacitors have been extensively exploited as an alternative energy storage technology in various fields such as electronics, computer, and mechanical. In this context, we have reported the utilization of the Ni–Co LDH/rGO nanostructure, deposited on the 3D conductive nickel substrate, to fabricate electrode for supercapacitor application. The film formed on the nickel substrate demonstrated superior electric conductivity and higher surface area which resulted in rapid electron transfer and more active mass deposition. Vertical nanorods grown on the rGO sheet was found to maximize electrode performance with a maximum specific capacitance of 2987 Fg−1at a current density of 1 Ag−1. The asymmetric supercapacitor was fabricated with Ni–Co LDH/rGO as a positive electrode and rGO as a negative electrode, which has rendered an energy density of 39.9 Wh/kg with a power density of 1.48 kW/kg1. Based on the obtained results, the fabricated supercapacitor is envisioned to be exploited in various potential applications.