Two-dimensional (2D) nanostructured materials such as graphene oxide nanosheets and molybdenum disulfide (MoS2) are potential candidates for electrochemical energy storage applications. The layered structure of MoS2 makes it a promising active electrode material for supercapacitors. Lithium (Li) interacted with MoS2/reduced graphene oxide (Li-MoS2/rGO) nanocomposite has been synthesized in two steps using a sonochemical dispersion method, and a one-pot hydrothermal method resulting in few-layered MoS2/rGO nanosheets of 2D heterointerfaces. The Li-MoS2/rGO nanocomposite exhibits a high specific capacitance of 173.3 F g−1 at a current density of 1 A g−1. Furthermore, an asymmetric supercapacitor device fabricated with Li-MoS2/rGO achieves a good energy density of 10.6 Wh kg−1 at a power density of 686.3 W kg−1 and outstanding cycling stability with 81.2 % capacity retention over 10,000 cycles. The dispersion of 2D-MoS2 in water is due to the strong electrostatic interface. The structural and electronic properties are theoretically calculated for pristine and Li-interacted MoS2/rGO heterostructure using density functional theory. A comparison of the density of states plots of the two heterostructures and the difference charge density plot of Li-MoS2/rGO heterostructure clearly brings out the importance of the presence of Li. A value of 64 μF cm−2 for the quantum capacitance for pristine MoS2/graphene heterostructure increases to a value 99 μF cm−2 corroborating the experimental observations and we assign this change to the transfer of charge from the Li atom to the outer S atoms in the MoS2/graphene heterostructure. This comprehensive approach, combining experimental synthesis with computational modelling, significantly advances the development and optimization of high-performance supercapacitor materials in the energy storage field. The Li-MoS2/rGO nanocomposite has excellent electrochemical specific capacitance and long-term cyclic stability and has been effectively used for supercapacitor applications with high electrochemical performance.