Single-crystal ZnS nanorods with tripod-like and tetrapod-like legs were synthesized by a simple thermal evaporation process on the Si substrate. The microstructures and properties of the as-synthesized products were analyzed by x-ray diffraction (XRD), scanning electron microscope (SEM) and photoluminescence (PL) measurements. The results show that the as-grown tripod-like nanorods have average diameters of 600 nm and the tetrapod-like nanorods have average diameters of 800 nm. The as-grown ZnS nanorods were perfectly single crystalline. A photoluminescence study shows a 429 nm emission peak from ZnS nanorods due to the self-activated luminescence.