Pure anatase TiO2 submicrotubes were successfully fabricated by a template-directed method. Electrospun poly(vinyl pyrrolidone) (PVP) fibers were used as a soft template for coating with titanium dioxide using an atomic layer deposition (ALD) technique. The deposition was conducted onto a template at 70 °C by using titanium tetraisopropyl oxide (TIP) [Ti(OiPr)4] and pure water as precursors of TiO2. Crystalline structure, microstructure, and optical properties of the TiO2 deposited layers before and after calcination were studied in detail. While the as-deposited TiO2 layers onto ES fibers were completely amorphous with thickness of about 60 nm, the TiO2 layers after calcination at 500 °C for 4 h were properly converted into polycrystalline nanostructured TiO2 submicrotubes with high quality of anatase. Thereby, the optical band gap energy was also tuned with a blue shift. As final products the self-supported free-standing mats consisting of pure anatase TiO2 submicrotubes can be easily handled and reclaimed for use in future applications related to catalysis, electronics, photonics, sensing, medicine, and controlled drug release. The free-standing, self-supporting TiO2 tubular mats consisting of pure anatase phase with well controlled thickness were successfully replicated from electrospun polymer fiber templates by atomic layer deposition. Due to their ultrahigh surface area and photosemiconducting behavior there is a great potential for future applications. [ABSTRACT FROM AUTHOR]