Large-scale synthesis of ZnS nanoawls was achieved by a simple two-step pressure-controlled vapor-phase deposition method. Awl-holders were well-rectangular faceted, and the diameter of the awl tips were in the range of 100−200 nm. High-resolution transmission electron microscopy shows that the nanoawls were single crystals growing along the [120] direction, which is different from the conventional [001] orientation. The optical properties of the ZnS nanoawls are also studied by Raman scattering and photoluminescence spectroscopy. The strong green emissions indicate that the nanoawls are promising for application in nanoscale optoelectronic devices. Furthermore, a possible two-stage growth mechanism of the ZnS nanoawls was also briefly discussed. By the suitable choice of source and synthetic parameters, it is reasonable to expect that the present synthesis route could be extended to obtain other semiconductor nanostructures.