Hierarchical hollow microspheres assembled by titanate nanotubes were fabricated via a hydrothermal process. During the entire process, the hydrous titanium oxide microspheres served as a template and source of titanate ions and H2O2 was used to facilitate the conversion of titanate sheets into nanotubes in low-concentration NaOH (0.1 M). Furthermore, this synthesis route is more friendly than the previous hydrothermal synthesis of TiO2-derived nanotubes in a highly alkaline (10-15 M) medium.