This paper reports a simple one-step hydrothermal route for the preparation of hierarchical nanosheets-based ZnO microstructures and their application to dye-sensitized solar cells. The morphologies of the products were controlled by the dosage of the reactants. Their physical characteristics were detected by X-ray diffraction, a field-emission scanning electron microscope and a surface analyzer. It is proved that the sample of ZnO microspheres with larger surface area and stronger light-trapping capacity since the superiority of their entirely spherical structures exhibits better photoelectrochemical properties than the mixtures of ZnO microspheres and ZnO microflowers. A dye-sensitized solar cell assembled by the ZnO microspheres as photoanode shows an energy conversion efficiency of 2.94% after surface modification by tetrabutyl titanate solution at 90°C. This result is over 1.6 times higher than the non-modified cell fabricated by the ZnO microspheres on the basis of the external improvement and the stability enhancement for the dye-sensitized ZnO photoanode.