For nuclear hydrometallurgical separation process development, it is necessary to demonstrate the stability of the extracting systems, since it is well known that radio- and hydrolytic degradation leads to undesirable effects, such as a decrease in selectivity, poorer phase separation and third-phase formation. Recently, we have developed a new family of bis-diglycolamide (bis-DGA) molecules with high distribution coefficients (D) for EuIII over AmIII. One of these bis-DGA extractants, namely, compound 1, showed high distribution coefficients even under gamma irradiation at 1000 kGy with external 60Co sources. We report herein a detailed account on the stability of 1against radio- and hydrolysis. We have also identified and quantified the sub-products formed during the irradiation process. Qualitative and quantitative analyses of irradiated 1 were performed by HPLC-MS, indicating the presence of seventeen degradation compounds. All fragments (2-18) were identified and synthesized independently. To complete this study, the AnIII and LnIII extraction properties of these fragments were assessed under the same experimental conditions as those used to evaluate the AnIII and LnIII extraction by irradiated 1. Despite the significance of a decrease in the concentration of 1, Am/Eu D values are still quite high. This means that at least some degradation products also act as efficient extractants. It is relevant to remark that two of the major degradation products (compounds 3 and11) are stable to radiation and showed high D values for AmIII and EuIII extraction.