Bio-oil is an important candidate to replace oil-derived products since it origins from renewable sources such as biomass. However, oxygenated bio-oil-based compounds require upgrading and further separation and purification for obtaining valuable compounds. Guaiacol is an important lignin derivative obtained from bio-oil, and it is a precursor for obtaining high-value-added molecules through heterogeneous catalysis. Alkanes are typical solvents for the guaiacol catalytical upgrading, so it is important to understand the extraction of guaiacol or guaiacol-like molecules from alkanes systems. This work reports the potential applicability of glycols and their corresponding eutectic mixtures with choline chloride as liquid–liquid extracting agents of guaiacol from n-hexane. The liquid–liquid equilibrium of six ternary systems composed of guaiacol + n-hexane + glycol or eutectic mixture is reported at 313.15 K and 101.3 kPa. Glycols selected as hydrogen bond donors were ethylene glycol, 1,2-propanediol, and 1,4-butanediol, while choline chloride was chosen as the hydrogen bond acceptor for preparing three eutectic mixtures using the glycols mentioned earlier. Density and viscosity of pure components and binary mixtures composed of guaiacol + glycols or guaiacol + eutectic mixture were measured at temperatures between 293.15 K and 333.15 K at 101.13 kPa. Density and liquid–liquid equilibrium data were modeled with PC-SAFT, and binary parameters were only used between the studied glycols and guaiacol. The results showed that the constituents of the eutectic mixtures did not distribute in the n-hexane phase, which was validated by NMR and GC. The viscosity of the pure components was correlated using PC-SAFT + Free Volume Theory, which allowed predicting the viscosity of mixtures by using binary parameters that were fitted to viscosity-independent data. The results obtained show that there is a high affinity between the guaiacol and the eutectic mixtures, based on observations about the negative excess volumes and the liquid–liquid equilibria. The eutectic mixtures are better for extracting guaiacol than their respective glycol-based constituents since they have higher selectivity and distribution coefficients and are larger miscibility gaps with the n-hexane phase compared to the studied glycols.