Pure titanium has been subjected to anodization in sulfuric and phosphoric acid. For a better understanding of the oxide growth and properties of the final film, with a particular interest focused on the solution anions in the early stage of crystallization, microstructural analyses (Raman, Transmission Electron Microscopy [TEM]) of the oxide films were correlated to chemical depth profiling by glow discharge optical emission spectroscopy (GDOES). Raman spectroscopy shows that crystallization of the oxide films starts at potentials as low as 10-20 V. The onset of crystallization and the ongoing increase in crystallinity with increasing anodization potentials had already earlier been correlated to ac-impedance measurements [Jaeggi et al., Surf. Interface Anal. 38 (2006) 182]. TEM observations show a clear difference in the early phase of crystallization between oxides grown in 1 M sulfuric acid compared to 1 M phosphoric acid. Moreover, independent of electrolyte type, nano-sized pores from oxygen bubbles formation were revealed in the central part of the films. Until now, oxygen bubbles inside an anodically grown oxide have not been observed before without the presence of crystalline regions nearby. A growth model is proposed, in which the different starting locations of crystallization inside the films are correlated to the presence of the acid anions as residues in the film, as found by GDOES chemical depth-profiling. (c) 2011 Elsevier B.V. All rights reserved.