Large-scale selective synthesis of uniform single crystalline tellurium nanowires with a diameter of 4-9 nm, and microbelts with a width of 250-800 nm and tens of micrometers in length, can be realized by a poly (vinyl pyrrolidone) (PVP)-assisted hydrothermal process. The formation of tellurium nanowires and nanobelts in the presence of PVP is strongly dependent on the reaction conditions such as temperature, the amount of PVP, and reaction time. The results demonstrated that the keys for selective synthesis of Te nanobelts and nanowires are to modulate the growth rates of (100), (101), and (110) planes in the presence of PVP and to precisely control the reaction kinetics. High-quality luminescent ultrathin t-Te nanowires with a diameter of 4-9 nm display strong luminescent emission in the blue-violet region. This approach provides a facile route for the production of high-quality tellurium nanostructures with an interesting optical property. Furthermore, the synthesized ultrathin nanowires with deep blue color and nanobelts in gray color by this approach can be well dispersed in water or ethanol, making it possible for further engineering of their surfaces to prepare other hybrid core-shell nanostructures.