BiOCl is a promising V-VI-VII-compound semiconductor with excellent optical and electrical properties, and has great potential applications in photo-catalysis, photoelectric, etc. We successfully synthesize BiOCl nanowire with a hierarchical structure by combining wet etch (top-down) with liquid phase crystal growth (bottom-up) process, opening a novel method to construct ordered bismuth-based nanostructures. The morphology and lattice structures of Bi nanowires, beta-Bi2O3 nanowires and BiOCl nanowires with the hierarchical structure are investigated by scanning electron microscope (SEM) and transition electron microscope (TEM). The formation mechanism of such ordered BiOCl hierarchical structure is considered to mainly originate from the highly preferred growth, which is governed by the lattice match between (1 1 0) facet of BiOCl and (2 2 0) or (0 0 2) facet of beta-Bi2O3. A schematic model is also illustrated to depict the formation process of the ordered BiOCl hierarchical structure. In addition, Raman properties of the BiOCl nanowire with the hierarchical structure are investigated deeply. (C) 2011 Elsevier B. V. All rights reserved.