In this work the suitability of selected commercially available hyperbranched polymers and ionic liquids as entrainers for the extractive distillation and as extraction solvents for the liquid–liquid extraction is investigated. Based on thermodynamic studies on the influence of hyperbranched polymers and ionic liquids on the vapor–liquid and liquid–liquid equilibrium of the azeotropic ethanol–water and THF–water systems, process simulations are carried out, which allow evaluating the potential of hyperbranched polymers and ionic liquids as selective components for the mentioned applications in terms of feasibility and energetic efficiency. Both hyperbranched polymers and ionic liquids break a variety of azeotropic systems. Since their selectivity, capacity, viscosity, and thermal stability can be customized, they appear superior to many conventional entrainers and extraction solvents. For the ethanol–water separation, the nonvolatile substances hyperbranched polyglycerol and [EMIM]+[BF4]− show a remarkable entrainer performance and therefore enable extractive distillation processes, which require less energy than the conventional process using 1,2‐ethanediol as an entrainer. Evaluation of a new THF–water separation process indicates the competitiveness of the suggested process and a considerable potential of using hyperbranched polymers as extraction solvents. © 2004 American Institute of Chemical Engineers AIChE J 50: 2439–2454, 2004