The wire-like Sb2Se3 microcrystallines can be synthesized via a simple PEG-400 polymer chain-assisted growth route in the temperature range of 160-180degreesC for 12-18 h in autoclave. X-ray power diffraction pattern gives the cell parameters of Sb2Se3 (a = 11.629 Angstrom, b = 11.779 Angstrom and c = 3.965 Angstrom), while the quantification of X-ray photoelectron spectra peaks gives the atomic ratio of the products as 2.27:3.00 for Sb:Se. Field emission scanning electronic microscope images show the as-obtained wire-like Sb2Se3 are with the typical lengths in the range of several tens micrometers, and selected area electronic diffraction pattern confirms the single crystal nature of the Sb2Se3 microwires. The chain structures of PEG-400 polymers are found to be morphology-directors on the growth process of the Sb2Se3 microwires. The pH, the reaction temperature and sodium tartrate are found to be key factors in the purity of the products. (C) 2003 Elsevier B.V. All rights reserved.