Crystal structures of titanate nanotubes prepared from a NaOH treatment of TiO(2) with subsequent acid washing were discussed from a viewpoint of vibrational spectroscopy. The correlation between the vibrational feature and the polymerization nature of the TiO(6) octahedron was established by analyzing Raman scattering data of crystalline TiO(2) (anatase and rutile) and layered protonic titanates. Then, the polymerization nature of TiO(6) octahedra in the titanate nanotubes was identified by comparing their Raman scattering spectra with those of the crystalline TiO(2) and layered protonic titanates. It demonstrated that the titanate nanotubes consist of two-dimensional TiO(6) octahedral host layers with a lepidocrocite (gamma-FeOOH)-type layered structure. This conclusion was confirmed further by considering the Raman scattering properties of a restacked titanate prepared by assembling TiO(6) octahedral layers derived from the original scroll-like titanate nanotubes. Our findings offered a convenient approach to validate the crystal structures of the products from an alkaline treatment of TiO(2) under different experimental conditions.