This study demonstrates how (Ni–Co–S)–reduced graphene oxide (rGO) heterostructure films influence the pseudocapacitance behavior of MoS₂ nanoflakes. rGO was produced through the electroreduction of CO₂ intermediates. The ordering of the heterostructure layers considerably impacted the morphology and interfacial bonding between the (Ni–Co–S)–rGO layers and MoS₂ nanoflakes. Electrodeposited (NiS/CoS)–rGO/MoS₂ and (CoS/NiS)–rGO/MoS₂ layers, prepared in two successive steps, exhibited a porous nanoplatelet structure, whereas the NiCoS–rGO/MoS₂ layers deposited in a single step formed dense nanocomposite (NC) films. X-ray photoelectron spectroscopy and Raman spectroscopy confirmed the presence of various surface bonding states (C–O/=O, S=O/–O, Ni/Co–S) between MoS₂ nanoflakes and (Ni–Co–S)–rGO layers, highlighting the development of synergy through diverse interfacial bonding states. Tailoring the nanoarchitecture of heterostructure layers led to variations in the electroactive site concentrations and charge transport kinetics. The (CoS/NiS)–rGO/MoS₂ nanoplatelets exhibited the highest specific capacitance of 3530.72 F∙g⁻¹ at 1 A∙g⁻¹, surpassing the (NiS/CoS)–rGO/MoS₂ nanoplatelets (3096.69 F∙g⁻¹) and NiCoS–rGO/MoS₂ NCs (2907.71 F∙g⁻¹). Asymmetric hybrid supercapacitors were assembled using the heterostructure (Ni–Co–S)–rGO/MoS₂ NCs and activated carbon (AC). The (CoS/NiS)–rGO/MoS₂ nanoplatelets//AC asymmetric supercapacitor achieved the highest energy density (E) of 26.69 Wh∙kg⁻¹ at a power density (P) of 302.7 W∙kg⁻¹, outperforming other heterostructure supercapacitors, and maintained an E of 9.36 Wh∙kg⁻¹ at a higher P of 2593.32 W∙kg⁻¹. The results illustrated that the in-situ formation of rGO species and the heterostructure layer configurations strongly influenced the pseudocapacitance performance of (Ni–Co–S)–rGO/MoS₂ hybrid electrodes.