Due to the presence of polysulfitabde shuttling, serious electrode expansion, and the low electrical conductivity of sulfur materials at room temperature, the commercialization of Li-S batteries is still not feasible. In this study, we have synthesized unique hollow molybdenum disulfide nanocages/reduced graphene oxide (H-MoS2/rGO) composites to be employed as highly effective cathodes for Li-S batteries. In this well-designed structure, the hollow MoS2 nanocages are tightly bound by C-O-Mo bonds and uniformly distributed across the graphene sheets. The dual-function MoS2 nanocages can adsorb polysulfides by Mo-S bond and accelerate the conversion reaction of S8 and Li2S. Moreover, the 3D rGO network with abundant pores effectively reduces the diffusion path and enhances the rapid transport of electrons and ions. The hybrid H-MoS2/rGO cathodes with these advantages exhibit a remarkable initial discharge capacity of 801.7 mAh g−1 at 1 C, as well as a high specific discharge capacity of 533.2 mAh g−1 is remained over 500 cycles.