The separation of trivalent actinides and lanthanides is a challenging task for chemists because of their similar charge and chemical behavior. Soft donor ligands like Cyanex-301 were found to be selective for the trivalent actinides over the lanthanides. Formation of different extractable species for Am3+ and various lanthanides (viz. La3+, Eu3+, and Lu3+) was explained on the basis of their relative stabilities as compared to their corresponding trinitrato complexes calculated using the density functional method. Further, the metal-ligand complexation energy was segregated into electrostatic, Pauli repulsion, and orbital interaction components. Higher covalence in the M-S bond in the dithiophosphinate complexes as compared to the M-O bond in the nitrate complexes was reflected in the higher orbital and lower electrostatic interactions for the complexes with increasing number of dithiophosphinate ligands. Higher affinity of the dithiophosphinate ligands for Am3+ over Eu3+ was corroborated with higher covalence in the Am-S bond as compared to the Eu-S bond, which was reflected in shorter bond length in the case of the former and higher ligand to metal charge transfer in Am(III)-dithiophosphinate complexes. The results were found to be consistent in gas phase density functional theory (DFT) calculations using different GGA functional. More negative complexation energies in the case of Eu3+ complexes of Me2PS2- as compared to the corresponding Am3+ complexes in spite of marginally higher covalence in the Am-S bond as compared to the Eu-S bond might be due to higher ionic interaction in the Eu3+ complexes in the gas phase calculations. The higher covalence in the Am-S bond obtained from the gas phase studies of their geometries and electronic structures solely cannot explain the selectivity of the dithiophosphinate ligands for Am3+ over Eu3+. Presence of solvent may also play an important role to control the selectivity as observed from higher complexation energies for Am3+ in the presence of solvent. Thus, the theoretical results were able to explain the experimentally observed trends in the metal-ligand complexation affinity.