Deep eutectic solvents (DESs) formed by choline chloride and urea or glycerol were tested for the separation of azeotropic mixtures. The case study was the separation of ethanol–ethyl propionate and n-propanol–n-propyl propionate. For this aim, the experimental data of liquid–liquid equilibria (LLEs) were obtained at temperature 293.15 K and atmospheric pressure. Liquid–liquid tie lines were determined using NMR spectroscopy and analyzed. The extraction performance of DESs was characterized with distribution coefficients and values of selectivity to alcohol. Comparison of selectivity values in systems containing alcohols and esters with another DES formed by choline chloride and malonic acid was carried out. The NRTL model for LLE data correlation was used. The model is shown to give rather good estimates for the selectivity values.