Three benzene-centered tripodal diglycolamides (Bz-T-DGAs) were synthesized and evaluated for actinide, lanthanide, and fission product ion extraction. 1,3,5-T riethylbenzene-based tripodal DGA (L_I)showed high distribution ratio (D) values for Am³⁺ and Eu³⁺ in a mixture of 95% n-dodecane and 5% iso-decanol at 3 MHNO₃. Eu/Am separation factors, in the range of 8–10, were obtained at 1 M HNO₃ which decreased at higher acidities with the exception of L_II which did not show much change. Benzene-1,3,5-triamide-based tripodal DGA (L_II) exhibited a high D -value for Pu⁴⁺ compared to the other ligands. Slope analysis showed the formation of 1 : 1 or 1 : 2 complexes is dependent on the ligand. The nature of the complexes was further studied with luminescence spectroscopy (Eu complexes) and DFT calculations (Am complexes).