An ionic-liquid-based aqueous two-phase system (iL-ATPS) consisting of an ionic liquid, tributylmethylammonium nitrate (N4441NO3), and NaNO3 aqueous solutions was developed for the extraction and separation of rare-earth ions, for example Nd(III), from transition-metal ions. The excellent selectivity of a green nonfluorinated ionic liquid and the low-viscosity feature of an aqueous two-phase system were combined in our suggested iL-ATPS. The results indicated that efficient separation of Nd(III) from transition-metal ions, Fe(III), Ni(II), and Co(II), could be obtained in our suggested iL-ATPS. Furthermore, different parameters of the separation process, including the concentrations of HNO3 and NaNO3 and the added amount of N4441NO3, were optimized. Notably, the extraction kinetics of Nd(III) could be improved significantly in the present iL-ATPS compared with the conventional organic-solvent-based ionic-liquid extraction systems. The similar environment across the liquid–liquid interface was revealed by ...