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