A low-cost and catalyst-free two-step approach has been developed to produce ZnO nanotubes (ZNTs) by simple thermal oxidation of Zn nanowires under 20 Pa at a low temperature of 400 °C. The growth mechanism of ZNTs is discussed in detail. The formation of these tubular structures is closely linked to the oxidation pressure and temperature, which involves a process consisting of the deposition of Zn nanowires, cracking of the Zn nanowires and sublimation of the Zn cores, and subsequent oxidation to ZNTs. The optical properties were studied by using Raman and photoluminescence spectra, where a strong green emission related to the single ionized oxygen vacancy appears. The photocatalytic activity measurement indicates an enhanced photocatalytic activity of the prepared ZNTs due to their high surface-to-volume ratios and abundant oxygen vacancies near the surfaces of the ZNTs. This type of high surface area structural ZNTs could find promising potential for optoelectronic and environmental applications.