Starting from the polymeric structure of Sb2S3, we successfully prepared sub-micron-sized hollow cones of Sb2S3 in a yield close to 85% via a solvothermal crystallization route. The quasi-2D ribbon-like structure of Sb2S3 can direct the formation of thin crystal flakes, which can transform into hollow cones through a spiral rolling-up process favored by the high pressure generated in the solvothermal environment. Techniques such as XRD, SEM, TEM, SAED, EDAX, and HRTEM were used to characterize their morphology, structure, and composition. This crystallization route is also workable for the preparation of tubular Bi2S3, and we believe that it could be extended to the preparation of novel tubes of other materials with an analogous chain structure, such as selenium and tellurium. (c) 2005 Elsevier B.V. All rights reserved.