In this work, the suitability or potential of ethanol aqueous solutions as a solvent for the extraction of alcohols from alcohol alkane mixtures was studied. Experimental liquid liquid equilibria (LLE) data of four quaternary systems {ethanol (1) + octanol (2) + dodecane (4) + water (6)}, {ethanol (1) + octanol (2) + tridecane (5) + water (6)}, {ethanol (1) + nonanol (3) + dodecane (4) + water (6)}, and {ethanol (1) + nonanol (3) + tridecane (5) + water (6)) were determined at T of 293.15, 298.15, and 303.15 K under atmospheric pressure. The nonrandom two-liquid model model was used to correlate binary interaction parameters. The parameters obtained from quaternary systems were used to predict six-component system LLE data. The predicted LLE data were in good agreement with the experimental data. The results showed that 75 wt % ethanol aqueous solution was suitable for separating octanol and nonanol from octanol + nonanol + dodecane + tridecane mixture and that 298.15 K was the suitable temperature.