Hierarchical Bi2S3 hollow spheres have been synthesized by a facile solvothermal process in the presence of sodium tartrate. The hollow spheres are composed of numerous ultrathin nanorods with the average diameter of 15 nm. Based on the time dependent electron microscope observations, the formation mechanism of such hierarchical structures has been proposed as a sodium tartrate directed self-assembled process and oriented attachement mechanism. The morphology and size of the subunits can be controlled by adjusting the amount of sodium tartrate. The Nitrogen adsorption-desorption measurements suggest that mesopores exist in these hollow spheres. The as-derived Bi2S3 hollow spheres exhibit excellent electrochemical hydrogen storage properties. Copyright (C) 2013, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.