A novel synergistic extraction system was investigated for the possible selective separation of light lanthanoids using an ionic liquid, 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, as an extraction solvent and 2-thenoyltrifluoroacetone and 18-crown-6 as extractants. Trivalent lanthanum was efficiently extracted as a cationic ternary complex by the cation-exchange process, whereas europium and lutetium showed relatively low extractability without forming respective ternary complexes. This result is thought to originate in a size-fitting effect of 18-crown-6 to lanthanum and the unique nature of the ionic liquid as a chelate extraction solvent.