The concentration of tetrabutyl titanate (TBT) and H2O influence on the reaction kinetics of TBT and acetic acid (AcOH) solvothermal system are systematically studied. It is found that TBT and H2O have greatly accelerated the hydrolysis-condensation process of the TBT-AcOH system. By adjusting those concentrations with reaction time, we prepare five kinds of sub-micron/micron precursors, which are hierarchical structures consisting of different primary building blocks. The morphology of these precursors varies from noninterlaced structures composed of flower-like microsphere and ellipsoid sphere to interlaced structures composed of flower-like microsphere interlaced nanofibers, ellipsoid spheres interlaced flower-like microsphere and nanoparticles interlaced flower-like microsphere. These interlaced structures are synthesized for the first time and are not ordinary mixtures of the noninterlaced structures. After heat treatment, these precursors are transformed to anatase TiO2. Shape-dependent photovoltaic performances of dye-sensitized solar cells (DSSCs) are also discussed. DSSCs based on these hierarchical sub-micron/micron TiO2 show 7.3%-7.9% energy conversion efficiencies, and the devices based on interlaced structures have higher efficiencies (7.4%-7.9%) than those of the devices based on noninterlaced structures (7.3%-7.6%). (C) 2013 Elsevier B.V. All rights reserved.