Lithium-sulfur (Li-S) batteries are promising next-generation energy storage because of their high theoretical energy density, low material cost, and environmental friendliness. However, commercialization faces significant challenges due to the cathode’s poor conductivity and the lithium polysulfide (LiPS) shuttle effect. During operation, highly soluble LiPSs, byproducts of sulfur reduction, dissolve into the electrolyte and migrate between the anode and cathode. This migration causes active material loss, reduced coulombic efficiency, and rapid capacity fading. Developing effective cathode host materials that can absorb polysulfides and prevent their diffusion is crucial. Two-dimensional (2D) materials such as graphene, molybdenum disulfide (MoS2), and vanadium disulfide (VS2) are attractive because of their high surface area, tunable physical and electrical properties, and strong affinity for sulfur species. Using first-principles methods, this study explores the potential of graphene/MoS2 and VS2/MoS2 heterostructures as effective cathode host materials by reducing the shuttle effect and thereby enhancing the cycling stability of Li-S batteries. We found that both graphene/MoS2 and VS2/MoS2 heterostructures show stronger adsorption for LiPSs than monolayer graphene, MoS2, and VS2. Stronger adsorption helps mitigate the shuttle effect while maintaining structural stability. The charge analysis further confirms strong chemical interactions between LiPSs and the host heterostructures. Ab initio molecular dynamics (AIMD) simulations reveal that the adsorbed configurations remain thermally stable under finite-temperature conditions. Our findings suggest that both graphene/MoS2 and VS2/MoS2 heterostructures are effective host materials to improve battery performance. This work provides fundamental insights and theoretical guidance for designing effective heterostructure electrode materials for next-generation high-performance Li-S battery applications.