Highly ordered hexagonal prism microstructures of copper sulfide (CuS) by assembling nano-flakes have been synthesized with high yield via a facile one-step route. We synthesized CuS microstructures using low cost beginning materials CuSO4 center dot 5H(2)O and Na2S2O3 center dot 5H(2)O under lower reaction temperature (60 degrees C). Hexamethylinetetramin (C6H12N4, HMT) was introduced into the reaction system as a capped agent. The influence of reaction time and capping agent (HMT) on the final structure of products was studied systematically. The obtained products were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), Energy-dispersive X-ray spectroscopes (EDS), and transmission electron microscopy (TEM). The possible mechanism for the formation of the interesting highly ordered hexagonal prism microstructures CuS was also proposed. (C) 2010 Elsevier B.V. All rights reserved.