Hierarchically nano-structured In2S3 hollow microspheres were synthesized by a hydrothermal method and the hollowing effect was attributed to an Ostwald ripening process. Using different amino acids as crystal growth modifiers, In2S3 with different surface morphologies, such as raspberry-like, urchin-like, and flower-like hollow microspheres, were selectively fabricated. The shells of the microspheres were composed of nanosized particles or nanoflakes of In2S3.These results demonstrate that amino acids with different functional groups, such as -NH2, -COOH, and -SH, can induce the formation of different indium sulfide nanostructures. A blue shifted UV band in the UV-Vis spectrum as well as a strong emission at ca 385 nm and a weak emission at ca 364 nm in the photoluminescence (PL) spectrum of In2S3 hollow microspheres indicate strong quantum confinement because of the presence of nanocrystalline particles. Using different amino acids as crystal growth modifiers, microspheres with different surface morphologies were fabricated. These results demonstrate that amino acids with different functional groups can induce the formation of different indium sulfide nanostructures.