Complexation of Np(V) with three structurally related amine-functionalized diacetamide ligands, including 2,2'-azanediylbis- (N,N'-dimethylacetamide) (ABDMA), 2,2'-(methylazanediyl)bis(N,N'- dimethylacetamide) (MABDMA), and 2,2'-(benzylazanediyl)bis(N,N'dimethylacetamide) (BnABDMA), in aqueous solutions was investigated. The stability constants of two successive complexes, namely, NpO2L+ and NpO2L2+, where L stands for the ligands, were determined by absorption spectrophotometry. The results suggest that the stability constants of corresponding Np(V) complexes follow the trend: MABDMA > ABDMA BnABDMA. The data are discussed in terms of the basicity of the ligands and compared with those for the complexation of Np(V) with an ether oxygen-linked diacetamide ligand. Extended X-ray absorption fine structure data indicate that, similar to the complexation with Nd3+ and UO22+, the ligands coordinate to NpO2+ in a tridentate mode through the amine nitrogen and two oxygen atoms of the amide groups. Computational results, in conjunction with spectrophotometric data, verify that the 1:2 complexes (NpO2(L)(2)(+)) in aqueous solutions are highly symmetric with Np at the inversion center, so that the f-f transition of Np(V) is forbidden and NpO2(L)(2)(+) does not display significant absorption in the near-IR region.