The complexation of Eu(III), Am(III) and Cm(III) with dicarboxylate anions with O, N or S donor groups was measured in I=6.60 mol⋅kg−1 (NaClO4) at temperatures of 0–60 °C by potentiometry and solvent extraction. The complexation thermodynamics of these complexes show that their stability is due to highly favorable complexation entropies because the complexation enthalpies are endothermic. Luminescence studies with Eu(III) and Cm(III) were used to measure the hydration numbers of the complexes. NMR spectra of 1H and 13C were used to determine the binding modes of La(III) with the ligands. The formation of 1:1:1 ternary complexes of M(EDTA)− with the dicarboxylate ligands was studied to determine changes in coordination of the metal cation with formation of the ternary species. The complexation of ternary complexes changes from bidentate to monodentate as the chain length between the binding sites of the dicarboxylates increases from 1 (malonate) to 4 (adipate). DFT computations were used to confirm the structural aspects of the interaction of these complexes.