Vertically grown TiO2-nanotubes (TiO2-NT) on a Ti metal substrate synthesized by electrochemical anodization followed by calcination have been studied using X-ray absorption near-edge structures (XANES) and X-ray excited optical luminescence (XEOL). It is found that the TiO2-NT system undergoes a series of phase transformations from amorphous (as-prepared) to anatase (400 °C) to rutile (>600 °C); the phase and morphology transformation is accompanied by unusual light-emitting properties, which are strongly dependent upon the crystal phase and morphology controlled by calcination temperatures, i.e. the as-prepared TiO2-NT exhibits no luminescence, whereas the anatase phase exhibits green luminescence, and an intense near-IR emission dominates in the rutile phase. The implications of these observations are discussed.