We demonstrate in this paper facile synthesis of CoS2 and NiS2 hollow spheres with various interiors through a solution‐based route. The obtained CoS2 microspheres constructed by nanosheets display a three‐dimensional architecture with solid, yolk‐shell, double‐shell, and hollow interiors respectively, with continuous changes in specific surface areas and pore‐size distributions. Especially, the CoS2 hollow spheres demonstrate excellent supercapacitive performance including high specific capacitance, good charge/discharge stability and long‐term cycling life, owing to the greatly improved faradaic redox reaction and mass transfer. Furthermore, CoS2 hollow spheres exhibit superior electrocatalytic activity for disulfide/thiolate (T2/T−) redox electrolyte in dye‐sensitized solar cells (DSCs). Therefore, this work provides a promising approach for the design and synthesis of structure tunable materials with largely enhanced supercapacitor behavior, which can be potentially applied in energy storage devices.