Semiconductor CuS hollow spheres by self-assembly coupled with bubble templating through a facile one-step solvothermal route has been demonstrated. An energy-minimizing-driven self-assembly of CuS nanoparticles on the base of H 2 S bubbles is responsible for the formation of the hollow structure. The as-obtained CuS products were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), energy-dispersive X-ray (EDX), and UV–vis–NIR spectrophotometer. Due to the unique optical property, these hollow structures are envisaged to be used in applications such as novel building blocks for the advanced materials, catalysis, solar cell devices, and drug delivery system.