The phase behavior of alkane/alcohol/ionic liquid ternary systems is essential for designing the separation process of alcohol from its mixture with alkane. In this work, 1-ethyl-3-metylimidazolium thiocyanate ([Emim] [SCN]) has been experimentally studied as an extractive agent for this process. New experimental liquid-liquid equilibria (LLE) data for four ternary systems (hexane/ethanol/[Emim][SCN], hexane/1-propanol/[Emim][SCN], hexane/2-propanol/[Emim][SCN], and hexane/1-butanol/[Emim][SCN]) are presented under standard conditions (pressure = 101.3 kPa and temperature = 298.15 K). The selectivity (S) and solute distribution coefficient (beta) are measured to investigate the effectiveness of ionic liquid as a solvent to separate alcohol from its azeotropic mixtures with hexane. Furthermore, the effect of alcohol chain length has been investigated. Finally, nonrandom two-liquid model is utilized and tuned to model the experimental LLE data.