Hierarchical chlorophytum-like Bi2S3 nanostructures are produced successfully on the large scale by a solvothermal method in the mixture of water and tetrahydrofuran. The crystal structure and morphology of the product are determined by X-ray diffraction (XRD) pattern, field emission scanning electron microscope (FESEM), and transmission electron microscopy (TEM). Time-dependent SEM observations indicate that the structure evolution of Bi2S3 contains self-assembly process and anisotropic growth mechanism. Furthermore, the electrochemical measurements present that the hierarchical Bi2S3 architectures display high electrochemical hydrogen storage and electrochemical Li intercalation performance. Copyright (C) 2013, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.