A simple and facile solution route has been developed for phase and morphology controllable synthesis of antimony trioxide (Sb2O3) microcrystals. Orthorhombic phase and cubic phase Sb2O3 microcrystals have been selectively synthesized in high yield. The products were characterized by powder X-ray diffraction (XRD) and scanning electron microscopy (SEM). The as-obtained microcrystals exhibited a variety of morphologies and structures, such as microspindles, nanoplates, and octahedra. Several experimental parameters have been investigated to gain morphology control of Sb2O3 microcrystals. Based on the time-dependent experimental results, an aggregation, and recrystallization mechanism was proposed to describe the formation process of these novel microstructures. (c) 2009 Elsevier B.V. All rights reserved.