A B S T R A C TOver the past ten years, self-aligned TiO 2 nanotubes have attracted tremendous scientific and technological interest due to their anticipated impact on energy conversion, environment remediation and biocompatibility. In the present manuscript, we review fundamental principles that govern the self-organized initiation of anodic TiO 2 nanotubes. We start with the fundamental question: Why is self-organization taking place? We illustrate the inherent key mechanistic aspects that lead to tube growth in various different morphologies, such as rippled-walled tubes, smooth tubes, stacks and bamboo-type tubes, and importantly the formation of double-walled TiO 2 nanotubes versus single-walled tubes, and the drastic difference in their physical and chemical properties. We show how both double-and single-walled tube layers can be detached from the metallic substrate and exploited for the preparation of robust self-standing membranes.Finally, we show how by selecting the "right" growth approach to TiO 2 nanotubes specific functional features can be significantly improved, e.g., an enhanced electron mobility, intrinsic doping, or crystallization into pure anatase at extremely high temperatures can be achieved. This in turn can be exploited in constructing high performance devices based on anodic TiO 2 in a wide range of applications.