The unusual uranyl peroxide studtite, [UO2(eta(2)-O-2)(H2O)(2)]center dot 2H(2)O, is a phase alteration product of spent nuclear fuel and has been characterized by solid-state cyclic voltammetry. The voltammogram exhibits two reduction waves that have been assigned to the U-VI/V redox couple at -0.74 V and to the U-V/IV redox couple at -1.10 V. This potential shows some dependence upon the identity of the cation of the supporting electrolyte, where cations with larger ionic radii exhibit more cathodic reduction potentials. Raman spectroelectrochemistry indicated that exhaustive reduction at either potential result in a product that does not contain peroxide linkers and is likely to be UO2. On the basis of the reduction potentials, the unusual behavior of neptunium in the presence of studtite can be rationalized. Furthermore, the oxidation of other species relevant to the long-term storage of nuclear fuel, namely, iodine and iodide, has been explored. The phase altered product should therefore be considered as electrochemically noninnocent. Radiotracer studies with Am-241 show that it does not interact with studtite so mobility will not be retarded in repositories. Finally, a large difference in band gap energies between studtite and its dehydrated congener metastudtite has been determined from the electronic absorption spectra.