ZnS hollow microspheres were prepared via a facile template-free chemical vapor deposition (CVD) route using metallic zinc powders and sulphur sublimed as reactants. The products were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and energy-dispersive X-ray spectrometer (EDX). The results showed that the as-prepared ZnS hollow spheres had uniform size about 4-8 mu m in diameter. The growth mechanism of such interesting was discussed. The optical property of the products was also recorded by means of photoluminescence (PL) spectroscopy. (C) 2007 Elsevier Ltd. All rights reserved.