Sb2O3 nanorod-bundles with length of about 4 mu m were fabricated in the presence of polyvinyl alcohol (PVA) by a simple hydrothermal method. The composition, morphology, microstructure and optical property of the as-prepared bundles were characterized by XRD, XPS, SEM, TEM and Raman spectrum. The results showed that the nanorod-bundles were composed of massive orthorhombic phase Sb2O3 nanorods grown along [0 0 1] direction. It was speculated that the nanorod-bundles developed through self-assembly of initially scattered nuclei into microdisks and subsequent oriented attachment process. PVA played a crucial role in the formation of Sb2O3 nanorod-bundles. (C) 2011 Elsevier B.V. All rights reserved.