Conventional distillation methods cannot effectively separate the components of an azeotropic mixture since both phases have the same composition, thereby preventing further separation. Additional techniques such as pressure swing distillation or distillation with entrainers are often employed to overcome this limitation and achieve separation. The aim of this investigation was to select the most effective method for separating n-hexane and ethanol. The feasibility of three methods was analyzed: reduced pressure distillation, extractive distillation, and liquid–liquid extraction. The mutual solubility of n-hexane and prepared deep eutectic solvents (DESs) (nine hydrophilic: choline chloride with glycerol, ethylene glycol, or carboxylic acid (malic, citric, glycolic); tetramethylammonium chloride with glycolic acid; lactic acid with glycerol; K₂CO₃ with glycerol or ethylene glycol; two hydrophobic: menthol with decanoic or dodecanoic acid) was experimentally determined. Extraction experiments were conducted to test the solubility of DESs in the feed mixture. The effect of changing DES-to-feed mass ratio was further investigated with choline chloride–glycerol (1:2). The same DES and both hydrophobic DESs were able to increase the relative volatility and enhance the separation of ethanol and n-hexane. Based on the obtained results, extraction was selected as the most effective method for the separation of n-hexane and ethanol.