In this letter, the formation of the hierarchical SnO 2 hollow octahedra was achieved by thermal treatment of ZnSn(OH) 6 precursors in ammonia solution. The synthesized SnO 2 was characterized by X-ray powder diffraction (XRD), field emission scanning electron microscopy (FE-SEM), and high resolution transmission electron microscopy (HR-TEM). The XRD pattern indicated the formation of well crystallized SnO 2 . The FE-SEM and HR-TEM images showed that the hollow octahedra were built by SnO 2 nanorod arrays. A possible formation mechanism for this kind of hollow octahedron structure was proposed. Room temperature photoluminescence shows that hierarchical SnO 2 hollow octahedra have two prominent emission bands at 575 and 625nm.