In this article, ZnO nanostructures were synthesized via the hydrothermal method which used ZnCl2 and HMTA mixed solution as the precursor. A multistep growth was adopted to improve the growth restriction of a closed system, not only the length but also the aspect ratio were increased with steps of growth, and the shape of nanorods maintained integrity. Furthermore, photoluminescence spectra which have the near-band-edge-emission (3.37 eV) and defect-related emission show the optical properties of ZnO nanostructures. The defect-related emission intensity was greatly enhanced with the increasing surface area of ZnO nanowires. The level of the OH group was attributed to the yellow-light emission (580 nm) and the red-shift phenomenon. In addition, we fabricated two types of ultraviolet photodetectors: a single nanowire device and a nanowire-array device, operating at a low bias (less than 5 mV). With the lower energy consumption and the weaker persistent photoconductive effect, our ultraviolet photodetectors have better performance, exhibiting a short response time and higher sensitivity.