Studies about the reaction of ZrIV ions with peroxides and the properties of the resulting zirconium peroxide clusters are significant for understanding zirconium chemistry in the nuclear fuel cycle and the advancement of less explored Group IV metal oxo clusters. Herein, an octanuclear zirconium peroxide cluster, designated as Zr8, was synthesized and characterized by using multiple techniques. Crystallographic analysis revealed that Zr8 has a ringlike structure and unusual positive charges, while tetravalent metal oxo clusters are mostly neutral. In situ variable-temperature Raman spectra indicated that Zr8 has unexpected thermal stability, which may be related to the strong interaction between ZrIV ions and peroxide groups. Small-angle X-ray scattering data showed that Zr8 self-assembled in the reactant solution prior to crystallization. In short, Zr8 expands the limited family of zirconium peroxide clusters and enriches the properties of metal peroxides.