Hierarchically macro-/mesoporous titanate tubular structures (HTT) self-assembled by nanotubes and nanosheets were fabricated by hydrothermal treatment of titanate glycolate rods in 0.1 M NaOH aqueous solution. Double-layered dye-sensitized solar cells (DSSCs) composed of a P25 nanoparticle (NP) underlayer and a tubular TiO(2) overlayer demonstrated an enhanced photovoltaic conversion efficiency of 6.2%.