Solubility equilibria of the chiral N-methyl-ephedrine species in two chiral ionic liquids, (S)-2-(methoxycarbonyl)pyrrolidinium bis(trifluoromethylsulfonyl) amide ([(S)-2-Pro-Me][NTF2]) and (1R,2S)-(-)-dimethylephedrinium bis-(trifluoromethylsulfonyl) amide, have been systematically studied. Solubility measurements were performed for [(S)-2- Pro -Me][NTF2] at temperatures between 278 and 308 K and ( 1R, 2 S)-(-)-dimethylephedrinium bis-(trifluoromethylsulfonyl) amide at 308 K, both with different initial enantiomeric compositions of N-methylephedrine. Methanol as a cosolvent was used to decrease the viscosity of [(S)-2-Pro-Me][NTF2]. The solubilities in [(S)-2-Pro-Me][NTF2] increased with temperature increments. A considerable asymmetry was observed in the ternary solubility phase diagram of the chiral N-methylephedrine and (IR,2S)-(-)-dimethylephedrinium bis(trifluoromethylsulfonyl) amide system. The accuracy of the solubility data for N-methylephedrine in (1R,2S)-(-)-dimethylephedrinium bis(trifluoromethylsulfonyl) amide at 308 K was ascertained by evaluating the mean absolute error.