Revealing the complexation behavior of high-valent actinides in solutions is of great importance to better understand the fundamental chemistry of actinides as well as to control the separation property of actinides in nuclear fuel cycles. In this work, the complexation of hexavalent actinide cations U(VI), Np(VI), and Pu(VI) with two dipicolinic acid derivatives, 6-(dimethylcarbamoyl)picolinic acid (DMAPA, denoted as HL) and N2,N2,N6,N6-tetramethylpyridine-2,6-dicarboxamide (TMPDA), in aqueous solutions were investigated by absorption spectrophotometry, X-ray crystallography, and DFT calculations. Formation of 1/1 and 1/2 (metal:ligand) complexes of U(VI), Np(VI), and Pu(VI) with DMAPA were identified and the corresponding stability constants were determined. The binding strengths of the three hexavalent actinide cations with DMAPA follow the order of U(VI) > Np(VI) > Pu(VI) in both 1/1 and 1/2 complexes, indicating that the driving force for the complexation is mainly electrostatic interactions. In addition, the relationships between the features of the absorption spectra and the symmetry of Pu(VI) and Np(VI) complexes with DMAPA have been established. The crystal structure of the 1/2 U(VI)/DMAPA complex as well as the DFT optimized structures of An(VI)/DMAPA complexes shed additional light on the structural characters of the hexavalent actinide cation complexes. In contrast to DMAPA, TMPDA exhibits no observable complexation with the three hexavalent actinide cations in aqueous solution, which could be attributed to low electron density on the donor atoms of TMPDA as well as steric hindrance effect by dimethyl carbamoyl groups as elucidated by DFT calculations. The results from this work provide new insights into the complexation trends of hexavalent actinide cations in aqueous solutions.