Three benzene-centred tripodal diglycolamide (Bz-T-DGA) ligands, where the diglycolamide (DGA) moieties are attached to a central benzene ring through ethylene spacers (LI), amide groups (LII) or ether linkages (LIII), were evaluated for their extraction behaviour towards trivalent actinide and lanthanide ions in a room temperature ionic liquid (RTIL), viz. 1-butyl-3-methylimidazolium bis(trifluoromethane)sulfonimide ([C4mim][Tf2N]). The extraction behaviour of these ligands in [C4mim][Tf2N] medium was compared with that obtained in the molecular solvent n-dodecane showing an opposite selectivity of LIII > LII > LIvs. LI > LII > LIII. In contrast to the n-dodecane medium, where a solvation extraction mechanism prevailed, a cation exchange mechanism was found to be operative in the RTIL medium. The stoichiometry of the extracted Am3+complex was found to be 1 : 2 (metal/ligand) and a nitrate ion was absent in the extracted complex. The luminescence spectroscopy of the Eu3+/ligand extracted complexes in the [C4mim][Tf2N] phase confirmed the absence of water molecules and that all the primary coordination sites of the metal ion are occupied by the ligands. The ligands display very large Pu/U, Am/U and Eu/U separation factor in the RTIL medium.