A new separation method of reactive extractive distillation is proposed for the separation of isopropanol and water, using the mixture of ethylene glycol (C2H6O2) and glycollic potassium (C2H5O2K) as an entrainer. Vapor-liquid-equilibrium (VLE) measurements confirmed that the entrainer was effective for this separation. Using a feed/solvent volume ratio of 1:1, isopropanol with a concentration over 96.0% weight fraction was obtained by the reactive extractive distillation process and the azeotropic point was eliminated. A novel process of separating isopropanol and water is designed on the basis of reactive extractive distillation to obtain the product with different concentrations, which may have a lasting value in industry.