Hierarchical molybdenum disulfide microspheres have been successfully prepared through a zinc ion-assisted hydrothermal route followed by an acid corrosion strategy. It is found that the MoS₂ microspheres comprised of numerous nanosheets with few-layered feature exhibit a 3D flower-like morphology. It is believed that the MoS₂/ZnS composites can act as a precursor for the formation of hierarchical MoS₂ microspheres. Additionally, the electrochemical properties of the as-prepared MoS₂ microspheres as an electrode material for supercapacitors have also been investigated. Compared with the MoS₂ nanosheet, the resultant MoS₂ microsphere demonstrates superior pseudcapacitive properties including high specific capacitance, good cycling and rate capability, which could be credited to its novel hierarchical architecture feature.