Uniform and ultralong single-crystalline tellurium (Te) nanowires with a diameter of 20 nm and length of tens of micrometers can be rapidly synthesized by a microwave-assisted method. The formation process of high-quality Te nanowires is strongly dependent on the reaction conditions such as the amount of polyvinylpyrrolidone (PVP), pH value of initial solution, reaction time, and the choice of surfactant. The hydrophilic Te nanowires display a broadened luminescent emission from shortwave ultraviolet to visible region excited by vacuum-ultraviolet (VUV) under synchrotron radiation at room temperature. Based on the examination of the chemical stability of the as-prepared Te nanowires stored in water, the relationship between the synthetic methodology and chemical stability of Te nanostructures has been discussed.