Hierarchical C@MoS₂ hollow spheres assembled from few layer-MoS₂ nanosheets coated on both interior and exterior surfaces of hollow carbon spheres (HCSs) have been developed by a modified template method. The polydopamine-derived carbon shell functions as a support with a negatively charged surface resulting in the in situ growth of few layer-MoS₂ nanosheets and prevents them from agglomeration with an integrated structure. In addition, the hollow carbon spheres with their mesopores provide sufficient liquid-solid contact area and shorter electron and ion pathways, as well as buffer for volume changes occurring during the charge/discharge process. The prepared C@MoS₂ material is characterized by XRD, TGA, BET, Raman, SEM, HRTEM and XPS measurements. When applied as a negative electrode material in LIBs, the C@MoS₂ electrode exhibits high reversible gravimetric capacity (1100 mAh•g^-1 at 0.1 C), superior rate performance (633 mAh•g^-1 at 20.0 C) and superb cycling life (86.0% of its original specific capacity left after 130 cycles).