Novel morphology titanate tubes were successfully synthesized via a self-assembly and self-removal process. After the product was treated by calcinating and washing, crystalline TiO2 tubes were obtained. In this study, two new concepts are applied to design the synthetic route: (i) titanium glycolate rods obtained from an ethylene glycol-mediated process and titanate sheets synthesized using the hydrothermal process were used as the template and the precursor, respectively, and ii) the template was directly removed in the reaction without posttreatment. Furthermore, a possible mechanism was proposed for the formation of tubular structures.