A tridentate diamide, N.N.N'.N'-tetraoctyldiglycolamide (TODGA) is very useful for the recovery of actinide ions from spent nuclear fuel Based on the mechanism of the radiolysis of TODGA in organic solution, an improvement of radiolytic stability of amidic extractants was attempted. The radiolytic degradation of TODGA was suppressed by the addition of appropriate compounds, due to reduction in the mole fraction of n-dodecane. In addition, by using the solvents having low ionization potentials, TODGA could be protected from radiation. Because the charge transfer reaction in the primary process was inhibited. It was also confirmed that aromatic substituents in the molecule effectively improved the radiolytic stability.