In this work, the liquid−liquid equilibrium (LLE) in the systems 1- propanol−1-propyl formate−deep eutectic solvent (DES) and 1-propanol−1-propyl propionate−DES at 293.15 and 313.15 K and atmospheric pressure was investigated. Three DESs were selected for this study: choline chloride (ChCl)/glycerol (Gl), ChCl/ ethylene glycol (EG), and ChCl/propylene glycol (PG). Quantitative analysis of coexisting equilibrium phases was carried out using proton nuclear magnetic resonance spectroscopy. The efficiency of separation of the systems 1-propanol−1-propyl formate and 1-propanol−1-propyl propionate using these DESs was evaluated by calculating the distribution coefficients and selectivity values. A comparative analysis of the selectivity values obtained in the work was carried out with data for other alcohol−ester systems and with other DESs presented in the literature. The accuracy of the experiment’s measurements was confirmed by the convergence of the obtained experimental data with calculations based on the non-random two-liquid equation (NRTL).