The assembly and hybridization of two-dimensional metal chalcogenides are recognized as an effective tactic to mitigate their stacking and low conductivity for achieving high-rate and durable lithium-ion batteries (LIBs). Herein, we demonstrate the synthesis and assembly of MoS2/rGO nanovesicles with the assistance of polystyrene nanospheres template. The unique vesicle-like nanostructure can greatly improve the infiltration of the electrolyte with abundant electroactive sites, thus leading to a shortened ions-diffusion path. Introducing rGO can not only enhance the conductivity but also avoid the restacking and pulverization of MoS2 during a long charge/discharge process. These advantages endow the MoS2/rGO nanovesicles with an improved rate capability (528 mAh g(-1) at 5 A g(-1)). They also possess superior cycling stability (almost without capacity loss after 200 cycles), much higher than MoS2/rGO nanosheets. More importantly, the MoS2/rGO nanovesicles are further assembled on flexible carbon cloth substrate by a simple dip-coating process, which also possess impressive electrochemical performance and mechanical strength, showing a huge potential for application in flexible energy storage devices.