Herein, well-defined hollow CuS microspheres assembled from nanosheets were successfully synthesized through a facile solvothermal method. Hollow CuS microspheres have an average diameter of 1.5 μm; moreover, the primary CuS nanosheets have an ultrathin thickness of about 10 nm and are bound by {0001} polar facets. When used as anodes for lithium-ion batteries (LIBs), hollow CuS microspheres exhibit excellent electrochemical properties, including a large discharge capacity (610.1 mAh g−1at 0.5 C), an excellent rate capability (207.6 and 143.4 mAh g−1at 1 and 5 C), and a superior cyclic stability (196.3 mAh g−1at 1 C after 500 cycles). When used as photocatalysts for Rhodamine B (RhB), hollow CuS microspheres can degrade more than 99% of the initial RhB within 21 min. These excellent Li-ion storage properties and photocatalytical performances are attributed to their unique hierarchical hollow structure.