A facile hydrothermal route has been employed to synthesize well-dispersed novel three-dimensional (3-D) flowerlike TiO2/MnO2 hierarchical architectures. The obtained products were characterized using XRD, SEM, TEM, and XPS. The experimental results indicate that the architectures are assembled by numerous square columns in an oriented manner at the center. A self-dassembly process is proposed to account for the formation of the obtained hierarchical structures.