The general approach to a novel class of functionalized ionic liquids 4-6 bearing grafted diphenylcarbamoylmethylphosphine oxide complexing groups in the cation has been elaborated. The synthetic route comprises the preparation of the intermediate (diphenylphosphorylmethylcarbamoyl)propylimidazole 3, followed by sequential quaternization by alkyl halides (chlorides or bromides) and anionic exchange in the case of ionic liquids bearing the hexafluorophosphate anion. The structures of two ionic liquids were confirmed by X-ray analysis, revealing the strong intramolecular hydrogen bond formed by the acidic protons of the heterocycle and oxygen atom either of the P=O or C=O group, depending on the anion nature. In neutral media, these ionic ligands form complexes ML(2) with europium chloride or europium nitrate via an O,O-bidentate mode similar to known neutral CMPO compounds. The solid phase extractants prepared by immobilization of these FILs on solid matrixes possess sorption activity towards actinides and rare-earth elements in nitric acid solutions.