The crystallization and morphology of brookite and anatase titania (TiO2) were controlled using the urea-mediated hydrolysis/precipitation route in the presence of the Ti3+ ions. Without the strong complexing agents and the non-hydrothermal conditions, simple alterations to the urea concentration led to the synthesis from brookite nanorods to anatase nanoflowers at a low temperature below 100°C, whereas the BET specific surface area evolved from 102 to 268m2 g−1, respectively. A possible formation mechanism was also proposed for these TiO2 nanostructures. The excellent reversible capacity and rate capability were achieved for the anatase nanoflowers because of the small crystallite size and significantly large surface area.