Poly(oxymethylene) dimethyl ethers (PODEn) are appealing additives for diesel fuels. Nowadays, the research on PODEn synthesis is crucial and essential, while the separation of PODEn from aqueous systems also has great significance for the production of PODEn in industry. In this work, ternary liquid-liquid equilibrium (LLE) data for the mixtures of (water + PODE1 + toluene), (water + PODE2 + toluene), (water + PODE3 + toluene), and (water + PODE4 + toluene) were determined at T = 293.15 and 303.15 K and p = 101.3 kPa. The consistency of experimental LLE data was evaluated by Hand and Othmer-Tobias equations. The distribution coefficients and separation factors were employed to assess the efficiency of extracting PODE1-4 from water. The experimental tie-line data of the studied systems were correlated using the Non-Random Two Liquid and Universal Quasi Chemical (UNIQUAC) activity coefficient models, while the corresponding binary interaction parameters were obtained with the results indicated that the UNIQUAC model gives a better agreement. All of the data demonstrated that toluene was an ideal extractant for separating PODE1-4 from aqueous solution.