Uniform Zn₂SnO₄/SnO₂ hollow spheres were successfully synthesized and hybridized by calcining ZnSn(OH)₆ solid spheres in air, and showed a very good efficiency of 4.52% as an electrode material for DSSCs. The in situ hybridization of Zn₂SnO₄ and SnO₂ in Zn₂SnO₄/SnO₂ hollow spheres is beneficial for electron transport and light scattering, and leads to the high efficiency of the Zn₂SnO₄/SnO₂ composite in DSSCs.