Highly ordered ZnS nanobundles were prepared using SBA-15 as a template and zinc ethyl xanthate as a single precursor. The nanobundles were characterized by transmission electron microscopy (TEM), thermal gravimetric-differential thermal analysis (TG-DTA), X-ray diffraction (XRD), N2 adsorption-desorption, ultraviolet-visible (UV-Vis) spectroscopy, fluorescence spectroscopy, and scanning electron microscopy (SEM). Results showed that ZnS nanobundles possessed a highly ordered hexa nal mesostructure and fiber-like morphology, analo us to the mother template. One of the ZnS nanobundles was aligned by an alternative current (AC) electric field assembly and the rectification performance for one of the ZnS nanobundles was characterized by a semiconductor characteristic measurement system. Results demonstrated that under UV illumination, the current-voltage (I-V) characteristics of ZnS nanobundles could be changed significantly and a ZnS nanobundle photoelectric switching effect was observed. The mechanism of the rectifying behavior and the photoelectric switching effect of the ZnS nanobundles are discussed.