Two new silica-based organic-inorganic hybrid materials (B104SGs and O104SGs) doped with a binary mixture of imidazolium and phosphonium ionic liquids have been synthesized and used as sorbents in batch system for rare earths (RE) separation. Imidazolium ionic liquids 1-butyl-3-methylimidazolium hexafluorophosphate (C(4)mim(+)PF(6)(-)) or 1-octyl-3-methylimidazolium hexafluorophosphate (C(8)mim(+)PF(6)(-)) acted as porogens to prepare porous materials and additives to stabilize extractant within silica gel. Trihexyl(tetradecyl)phosphonium bis(2,4,4-timethylpentyl)phosphinate (Cyphos IL 104), a low-molecular-mass organic gelator, can encourage the formation of porous silica materials and increase the rate of aggregation. Cyphos IL 104 not only acted as an excellent template for the preparation of silica sorbents but also as a bifunctional ionic liquid extractant (bif-ILE) for RE(III) extraction. By the electrostatic attraction between the SiO- groups and phosphonium cations along the surfaces of the silica gel, stable silica sorbents with high extractant content were formed.