The significance of understanding the interaction between actinide(III)/lanthanide(III) (An(III)/Ln(III)) and N-donor extractants lies in the importance of efficient An(3+)/Ln(3+) separation in advanced nuclear fuel cycles and the high expectation of the application of N-donor extractants. This work reports a density functional theory study aiming at a plausible explanation of the origin of the selectivity of the ligands in An(3+)/Ln(3+) separation and an evaluation of the influence of the bridging groups of typical N-donor extractants. Five bis(triazine) N-donor ligands were considered, differing in their denticity dictated by their bridging groups and in the flexibility of these bridging groups. The results showed much stronger hydration of Eu(III) in comparison to Am(III) in the ligand exchange of aqua ligands by N-donor ligands, while there was a moderate difference in their interaction strengths with the N-donor ligands. This implicated that the distinct difficulty in desolvating Eu(III) and Am(III) may govern their selectivity in liquid-liquid extraction. The analysis of the role of the bridging groups of the ligands confirmed the importance of a ligand to be equipped with preorganized binding sites to minimize the perturbation of entropy. We tentatively propose that this conclusion may hold in the explanation of the low selectivity of oxygenated extractants and the high selectivity of extractants with soft donors in An(3+)/Ln(3+) separation.