Novel yolk-shell-like TiO2 hierarchical microspheres (YSTHSs) were synthesized by a facile one-pot hydrothermal method. These YSTHSs exhibited excellent light scattering ability and high specific surface area for more dye adsorption. A YSTHSs multifunctional scattering layer was fabricated on top of a conventional TiO2 nanocrystalline layer (T) to form a heterostructure bilayer photoanode (T-YSTHS). The influences of the YSTHSs on the properties of the photoanode and dye-sensitized solar cell (DSSC) were investigated. Studies indicated that by introducing the YSTHSs, the light scattering, dye loading, electron mobility and lifetime of this bilayer photoanode were remarkably increased, resulting in the great enhancement in the short-circuit current density (J(sc))and thus the photoelectric conversion efficiency (PCE) of the DSSCs. This T-YSTHS based DSSC exhibited the maximum J(sc) of 16.35 mA cm(-2) and PCE of 6.01%, remarkably higher than those of the conventional TiO2 nanocrystalline (2T)-based DSSC by 27.1% and 20.4%, respectively. The remarkable enhancement in Jsc and PCE for the T-YSTHS-based DSSC compared to the 2T-based DSSCs are mainly attributed to the significant enhancement in light scattering and the increase in the specific surface area for dye adsorption due to the unique yolk-shell hierarchical microsphere structure of the YSTHSs. (C) 2014 Elsevier B.V. All rights reserved.