Well-faceted hexagonal ZnO nanotubes were synthesized by a simple hydrothermal method and the subsequentaging process without any catalysts or templates. The formation of the tubular structure is closely linked tothe polarity of ZnO and the selective adsorption behavior of Zn2+ amino complexes. The surface-relatedoptical properties were studied with use of Raman and photoluminescence spectra. It was found that theoxygen vacancy-related visible emission intensity decreased while surface defect-related visible emissionintensity increased when the nanotubes were annealed in oxygen ambient. The anomalous enhancement ofPL integrated intensity with the temperature shows fairly high surface state density existing in ZnO nanotubes.