Leaching / Radiolysis / XPS / alpha-doped UO 2 / PlutoniumSummary. Corrosion and dissolution of UO 2 doped with short-lived α-emitters, the so called α-doped UO 2 , was investigated in leaching experiments combined with X-ray Photoelectron Spectroscopy (XPS) analyses. These experiments are part of an ongoing set of tests aiming at evaluating the effects of α-radiolysis on the dissolution of the UO 2 spent fuel matrix when it will become exposed to groundwater in a deep final repository. Pellets of UO 2 containing ∼ 10 and ∼ 0.1 wt. % 238 Pu were used. These compositions simulate the α-radiation field of different types of commercial LWR spent fuel after different storage times. Undoped UO 2 pellets were also used as reference. Static sequential leaching experiments in demineralised water at room temperature under anoxic conditions confirmed that higher fractions of uranium are released in the case of α-doped materials compared with undoped UO 2 . Relatively large amounts of plutonium were found in the leachate of the materials doped with 238 Pu. Significant contributions to the total amount released of uranium were found in the rinse solutions of the leaching vessels.