This study assessed the effect of ionic liquids (ILs) on extraction of 2-phenylethanol (PEA) from aqueous phase. It consists the synthesis of four new ILs, their physicochemical properties, and experimental solubility measurements in water as well as liquid-liquid phase equilibrium in ternary systems. ILs are an important new media for imaging and sensing applications because of their solvation property, thermal stability, and negligible vapor pressure. However, complex procedures and nonmiscibility with water are often required in PEA extraction. Herein, a facile and general strategy using four ILs as extraction media including the synthesis of new bis(fluorosulfonyl)imide-based ILs, 1-hexyl-methylmorpholinium bis(fluorosulfonyl)imide, [HMMOR][FSI], N-octylisoquinolinium bis(fluorosulfonyl)imide, [OiQuin][FSI], 1-butyl-1-methylpyrrolidinium bis(fluorosulfonyl)imide, [BMPYR][FSI], and N-triethyl-N-octylammonium bis(fluorosulfonyl)imide, [N-2228][FSI], were investigated. The thermal properties, density, viscosity, and surface tension of new ILs were measured. Calorimetric measurements (DSC) were used to determine the melting point and the enthalpy of melting as well as the glass transition temperature and heat capacity at glass transition of the ILs. The phase equilibrium in binary systems (IL + PEA, or water) and in ternary systems {IL (1) + PEA (2) + water (3)} at temperature T = 308.15 K and ambient pressure are reported. All systems present liquid-liquid equilibrium with the upper critical solution temperature (UCST). All ILs revealed complete miscibility with PEA. In all ternary systems immiscibility gap was observed, which classified measured systems as Treybal's type II. The two partially miscible binaries (IL + water) and (PEA + water) exist in these systems. The discussion contains the specific selectivity and the solute distribution ratio of separation for the used ILs. The commonly used NRTL model was used for the correlation of the experimental binary and ternary systems with acceptable root-mean-square deviation. The prediction of binary and ternary compositions was provided with acceptable deviations using COSMO RS. The data of ternary LLE show the possible use of [HMMOR][FSI] as a good entrainer for the separation of PEA from water using solvent extraction.