The highly selective nitrogen donor ligand CyMe4BTBP for An(III) separation by solvent extraction was irradiated in a 60Co γ-source under varying conditions. Organic solutions of 10 mmol/L ligand in 1-octanol were contacted with different concentrations of nitric acid to observe the influence of an aqueous phase during irradiation. In subsequent liquid-liquid extraction experiments, distribution ratios of 241Am and 152Eu were determined. Distribution ratios decreased with increasing absorbed dose when irradiation was performed in the absence of nitric acid. With addition of nitric acid, initial distribution ratios remained constant over the whole examined dose range up to 300 kGy. For qualitative determination of radiolysis products, HPLC-MS measurements were performed. The protective effect of nitric acid was confirmed, since in samples irradiated with acid contact, no degradation products were observed, but only addition products of the 1-octanol molecule to the CyMe4BTBP molecule.