The distribution constants of 4-benzoyl-3-phenyl-5-isoxazolone (HPBI) and deprotonated one (PBI-) between hydrophobic ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ([C(1)C(4)im][Tf2N]) and aqueous phases were determined, together with the acid-dissociation constant of HPBI. The solvent extraction of three selected lanthanoid ions (La3+, Eu3+, and Lu3+) with HPBI from aqueous nitrate phase into [C(1)C(4)im][Tf2N] has been investigated. Application of the ionic liquid as the extracting phase greatly enhanced the extraction performance of HPBI for lanthanoid ions compared with that in the chloroform system. A slope analysis was conducted in order to compare the results of the solution 4f-ion coordination chemistry in ionic and molecular media. The composition of the extracted species was established to be anionic tetrakis entities, Ln(PBI)(4)(-), for light, middle, and heavy lanthanoid ions in an ionic environment (Ln denotes lanthanoid ion). Nevertheless, the typical neutral chelate lanthanoid complexes of the type Ln(PBI)(3) have been detected when the conventional molecular diluent chloroform was applied as an organic phase.