Leaching experiments were done on UO2 pellets doped with alpha-emitters (238/239Pu, 1500 - year batch), in the presence of an external gamma irradiation source (A60Co = 260 Ci, γ dose rate = 650 Gy h−1). The effects of α and γ radiation and the nature of the cover gas (air or Ar + 4% H2) on water radiolysis, and on oxidizing dissolution of the UO2 matrix, are quantified and discussed. The cover gas clearly has a major role in the effect of γ radiolysis. The dissolution rate in an aerated medium is 83 mg m−2 d−1 compared with only 6 mg m−2 d−1 in Ar + 4% H2. The rate drop is accompanied by a reduction of about four orders of magnitude in the hydrogen peroxide concentrations in the homogeneous solution. The UO2 alteration rate under gamma radiation in Ar + 4% H2 is comparable to the rate obtained in the presence of alpha radiolysis alone for the doped UO2 pellets with the highest alpha activities (4.75 × 108 Bq/g UO2, 15 - year batch).