Patterned polystyrene (PS) nanotube arrays were successfully fabricated using photolithography via the polymer solution-wetting method. The microstructure of these nanotubes was investigated using conventional and high-resolution transmission electron microscopy (HRTEM). Two major types of morphology were observed for these PS nanotubes, one being bamboo-like and the other being barrel-shaped. The multiwetting mechanism was proposed to explain the different morphologies. X-ray diffraction (XRD) showed that the PS nanotubes have a higher degree of crystallinity than bulk PS. In addition, crystalline lattice fringes were observed in some regions of the PS nanotubes using HRTEM. Patterned polymer nanotube arrays could be used for nanocable coating to protect from oxidation and corrosion in nanodevices.