The recovery and separation of trivalent lanthanides into individual elements is difficult owing to their similar chemical behaviours. In this study, the solvent extraction of trivalent lanthanide ions from nitric acid solutions in an organic phase comprising a mixture of two electrically neutral extractants, viz. tri(n-butyl)phosphate (TBP) and N,N,N′,N′-tetra(n-octyl)diglycolamide (TODGA), is investigated. The hydrophobic room-temperature ionic liquid (IL), 1-methyl-3-butyl-imidazolium bis(trifluoromethanesulfonyl)imide, is employed as a more environmentally benign diluent compared to the conventional molecular solvents. The results reveal that the addition of TBP as a co-extractant with TODGA not only significantly enhances the metal ion extraction but also affords high intra-lanthanide ion selectivity. This is attributed to the formation of complex lanthanide species with both TBP and TODGA. In addition, when IL is used as a diluent, the cationic exchange between metal–organic ligand species and IL cations, as well as neutral complex extraction result in a more efficient extraction. Moreover, the hydrophobic anionic IL entities can also be involved in the extraction mechanism, affording lipophilic metal–organic ligand complexes. The synergistic solvent combination of TODGA, TBP, and IL can afford an excellent separation of the lanthanide(III) ions.