ZnSn(OH)6 hierarchical cubes and Zn2SnO4 octahedra have been synthesized through a rapid, template-free, one-pot hydrothermal approach using zinc acetate, tin chloride and sodium hydroxide. ZnSn(OH)6 aggregates with cubic morphology and uniform size distribution have been successfully synthesized via aggregation-mediated crystallization. Through adjusting the hydrothermal parameters, Zn2SnO4 octahedra were obtained at a higher temperature. The formation of Zn2SnO4 octahedra undergone a transformation from ZnSn(OH)6 cubes. The as-synthesized products were characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM) and differential scanning calorimetric analysis (DSC) and thermogravimetric analysis (TG).