The cube-like TiO2 mesocrystalline hollow boxes (TiO2-MHBs) are fabricated by a topotactic transformation method. TiO2-MHBs consist of one-dimensional nanorod-like rutile TiO2 combined with anatase TiO2. The ordering of TiO2-MHBs is in favor of efficient electron transport. TiO2-MHBs with mesoporous structure show excellent light scattering performance. Dye-sensitized solar cell with TiO2-MHBs light scattering overlayer exhibits an 18.3% increment of cell efficiency (9.51%) compared with the TiO2 nanoparticles film cell (8.04%). The improved photovoltaic performance is attributed to its unique crystallographic property and highly porous structure, which can enhance light scattering capability, quicken electron transport and electrolyte diffusion, and reduce charge recombination. (c) 2021 The Society of Powder Technology Japan. Published by Elsevier B.V. and The Society of Powder Technology Japan. All rights reserved.