We report on the formation of hexagonally ordered TiO2 nanocolumnar layers by electrochemical oxidation in a fluoride containing electrolyte, using self-organizing nanotube formation conditions at elevated potentials and low temperatures. The influence of the substrate temperature on the nanocolumn morphology and composition is investigated and characterized by FE-SEM and EDX. The origin of these nanocolumns can be attributed to a thickening of the inner tube wall of the double wall structure of self-organized TiO2 nanotubes. Furthermore, a transition from nanocolumnar to nanotubular structure can be established by changing the applied voltage or applying a post-immersion treatment. (C) 2011 Elsevier B. V. All rights reserved.