Single-crystalline nanostructured Zn 1−x Mn x S, a diluted magnetic semiconductor, was achieved via a simple vapour phase deposition on silicon substrates. Morphology, structure, and composition of the nanostructured Zn 1−x Mn x S were studied by using x-ray diffraction, transmission electron microscopy, and energy-dispersive spectroscopy. The nanostructured Zn 1−x Mn x S is composed of nanowires and nanobelts, which are quite flexible and free of defects. Both of them have smooth and straight surfaces with lengths over 10 µm. They possess cubic structure with a principal axis 111 along their axes. The nanostructured Zn 1−x Mn x S exhibits paramagnetic behaviour. Photoluminescence study shows a blue band and a yellow band, which are due to the surface states and the transitions of Mn 2+ ( 4 T 1 (G)-6 A 1 (S)), respectively. The growth of the nanostructured Zn 1−x Mn x S could be explained by a self-catalyst growth mechanism.