Acetohydroxamic acid (AHA) is a novel salt-free reagent used for the separation of Pu and Np from U in the advanced Purex process. This paper reports the γ-ray damage of AHA in HNO3 and its radiolytic product. For 0.2 mol L−1 AHA in 0.2–2.0 mol L−1 HNO3 irradiated at a dose of 5–25 kGy, the radiolytic rate of AHA is 6.63–77.5%, and it increases with the HNO3 concentration and absorbed dose. The main radiolytic gases are N2O and H2, with volume fractions of (0.500–16.2) × 10−2 and (1.30–11.8) × 10−3, respectively, and they increase with the absorbed dose; the H2 volume fraction decreases with increasing HNO3 concentration. The main liquid radiolytic products are CH3COOH and HNO2, and their concentrations are (3.40–19.7) × 10−2 and (0.200–4.80) × 10−3 mol L−1, respectively, which increase with the HNO3 concentration. Since a significant concentration of HNO2 is present in the irradiated AHA-HNO3 solution, a holding reductant must be used to destroy HNO2 and stabilize Pu(III) and Np(V) when AHA is applied for the separation of Pu and Np from U.