Hollow spindle-like and cobblestone-like Sb2O3 microstructures, have been successfully synthesized via a hydrothermal method by using cetyltrimethylammonium bromide (CTAB) as soft-templates. Results from XRD, SEM, TEM, Raman and BET showed that experimental parameters, such as the reaction temperature and time, played crucial roles in the respective morphological control of Sb2O3 microstructures. On the basis of these results, possible growth mechanisms for the formation of hollow spindle-like and cobblestone-like microstructures are presented and discussed. (C) 2010 Elsevier B.V. All rights reserved.