The performance of hybrid supercapacitors (HSCs) can be increased via the selection of higher capacitive electrode materials. Thus, layered double hydroxides (LDHs) have received extensive consideration in HSCs owing to their good ion-exchange properties, structural flexibility, and large specific surface area. Ni–Co-based LDHs show better specific capacitance, good synergy, and high-rate capability in aqueous electrolytes. However, LDHs suffer from low conductivity, which curbs the charge transfer and mass diffusion throughout the electrochemical process. Thus, the high performance of LDH-based supercapacitors is impeded. Hence, composites of LDH and conducting materials are used. Owing to its extraordinary conducting property, huge surface area, and cost-effectiveness, reduced graphene oxide (rGO) is used as conducting material for LDH-based composite electrodes. Moreover, via the incorporation of heteroatoms (N, S, etc.) into rGO, its electrochemical properties are further enhanced. Here, a novel composite electrode is prepared by wrapping Ni–Co-LDH with N and S-co-doped rGO (LDH-rGO-NS) via a hydrothermal process. The XPS C 1s spectra established the existence of N and S doping in the rGO. The electrochemical performance is enhanced due to an excellent ion/charge transfer rate because of N and S co-doping. The LDH-rGO-NS electrode offers a good charge transfer resistance of 0.24 Ω. The obtained anodic and cathodic b-values are 0.73 and 0.72, respectively. An admirable specific capacitance of 1388 F g⁻¹ is accomplished at a sweep rate of 100 mV s⁻¹. Furthermore, the obtained retention capacity is ∼71% after 2000 cycles. Moreover, the achieved specific capacitance is 2193 F g⁻¹ at the discharge current density of 5 A g⁻¹. The excellent electrochemical properties reveal the LDH-rGO-NS composites as encouraging electrode materials for HSCs.