Radiolytic degradation is an important aspect to consider when developing a ligand or a complexant for radionuclides. Diglycolamide extractants (DGAs) have been playing an important role in many partition processes for spent nuclear fuel. In particular, the extractant N,N,N′N′-tetraoctyl diglycolamide (TODGA) has been studied intensively for the purpose of solvent extraction processes such as ARTIST, i-Sanex, EURO-GANEX and EURO-EXAM, which have been developed around the TODGA extractant. For the first time, the radiolytic stability of TODGA was investigated both by in situ alpha irradiation using a macroconcentration of americum(III) and by ex situ gamma irradiation in the presence of a macroconcentration of neodymium(III). It was shown that metal ions complexed in the organic phase protect TODGA from degradation by irradiation and that the degradation was slower using in situ alpha irradiation compared to ex situ gamma irradiation. By comparison to gamma irradiation of Nd–TODGA solution, alpha irradiation of Am–TODGA solutions showed the presence of 2 additional compounds identified as a TODGA molecule with a CC bond and a TODGA molecule with the addition of a NO₃ group. The major degradation products were identified and a degradation schema was proposed. The direct analysis of the solution containing Am(III) or Nd(III) showed that the degradation compounds retaining a diglycolamide skeleton are involved in heteroleptic complexes with TODGA, without a negative impact on An(III) or Ln(III) complexation.