Hierarchical CoS2 hollow nanospheres (HSs) with a nitrogen-doped-carbon coating (NC@CoS2) are fabricated by a simple solution method. The uniform 300 nm-sized NC@CoS2 HSs are composed of ultrathin nanosheet subunits with a thickness of around 2 nm. It was found that polyvinylpyrrolidone and ethylenediamine not only controlled the morphology of the products, but also provided the sources of nitrogen-doped carbon. Benefiting from their unique structural characteristics, hierarchical NC@CoS2 HSs can be applied in lithium-ion batteries, supercapacitors, and photocatalysis. When evaluated as an electrode material, NC@CoS2 with a coating of optimal thickness showed a high lithium-storage capability with a good cycling stability. Moreover, NC@CoS2 had a remarkable supercapacitive performance and photocatalytic activity. The attractive electrochemical and photocatalytic performances were attributed to the overall structural features of the NC@CoS2 hollow spheres: the N-doped-carbon (NC) coating, hollow interior, and ultrathin nanosheets.