This paper describes an ethylene glycol (EG)-assisted approach to the large-scale ultralong Sb2S3 sub-microwires, formed by a simple hydrothermal reaction between SbCl3 and Na2S in the presence of distilled water. Transmission electron microscopy and simple hydrothermal reaction between electron microscopy studies indicate that these Sb2S3 sub-microwires possess a diameter around 200 nm and length up to 100 mu m. High-resolution transmission electron rnicroscopy and selected area electron diffraction studies reveal that each Sb2S3 sub-microwire is a single-crystal along the [0 0 1] direction. The possible formation mechanism of the sub-microwires was discussed. The effects of volume ratio of EG/water, reaction temperature and the concentration of CO(NH2)(2) on the morphology of Sb2S3 sub-microwires were also investigated. (C) 2007 Elsevier Ltd. All rights reserved.