S-doped ZnO natostructures such as nanonails and nanowires have been synthesized via a simple one-step catalyst-free thermal evaporation process on a large scale. The doping concentration of sulfur into ZnO nanonails and nanowire were 2 atm % and 7.5 atm %, respectively. Studies found that the S-doped ZnO nanonails and nanowires were single-crystalline wurtzite structure and grew along the (001) direction. The average diameters of the nanonails and nanowires were 70 and 50 nm, respectively. Low-temperature photoluminescence spectra of ZnO samples showed two luminescence peaks in the UV and green emission region, respectively. As the concentration of sulfur in the ZnO nanostructures increased, the intensity of the UV emission peak decreased dramatically, and it showed a little blue-shift while the intensity of the green emission increased greatly.