Abstract The morphology, microstructure and crystallography of titanium dioxide (TiO 2 ) have great effect on the photoelectric performance of dye-sensitized solar cells (DSSCs). Herein, flower-like 3D TiO 2 microstructures based on well-defined high-crystalline nanosheets are synthesized through a facile hydrothermal method. Especially, morphological evolution process and mechanism of this hierarchical structure are investigated. Due to the highly crystalline nature and smaller surface area of these nanosheets, the corresponding device shows an extremely high open-current voltage up to 0.84 V, which results from the less electron recombination. When applied as a scattering layer on top of the nanoparticle layer, the power conversion efficiency (PCE) can be significantly improved and give birth to a PCE value of 9.6%, which is 24.6% higher than that of an analogous device using nanoparticles (NP) (7.7%). As reflected by diffusion reflection spectra, intensity of the modulated photocurrent/photovoltage spectroscopy (IMPS/IMVS) and electrochemical impedance spectra (EIS), this hierarchical structure can not only enhance light harvesting, but also reduce electron recombination, facilitate electron transport and improve electron collection efficiency.