UO2 containing short-lived α-emitters, the so-called α-doped UO2, can simulate type (i.e. α- decay) and level of activity of spent fuel at the time when it might become exposed to groundwater in a geologic repository during storage. This allows studying α-radiolysis effects on the dissolution of the fuel matrix. Additionally, UO2 with high concentrations of α-emitters accumulate, during experimentally acceptable short times, the amount of decays, hence of property modifications, corresponding to long storage times for spent fuel. UO2 containing ∼10 and ∼0.1 wt% 238Pu was fabricated and tested. Leaching experiments in deionized water under unaerated conditions, with continuous monitoring of the evolution of the redox potential and pH in the leaching solutions, were performed. The Eh measurements showed a fast increase of the redox potential in the case of the material with the highest α-activity, while the UO2 containing ∼0.1 wt% 238Pu increased its potential more slowly. The redox potential for undoped UO2 decreased steadily during the experiment. As previously observed, higher fractions of U were released in the case of α-doped UO2 compared to undoped UO2. The fractions of U and Pu released during leaching from the α-doped materials were very similar, suggesting that congruent dissolution occurred. After leaching times longer than 10 h, only dissolved species were present in the solutions. Under these experimental conditions, characterized by relatively low values of the ratio sample surface/leachant volume, a dependence of the released amounts on the α-activity of the samples was observed. Periodical measurements of parameters like hardness, showed a rapid buildup of radiation damage in the material with the high α-activity. After more than two years, noticeable changes, namely an increase of the hardness, have begun to be observed also for the material with the low concentration of 238Pu.