In this study, densities for binary mixtures of {1-Ethyl-3-methylimidazolium thiocyanate ([EMIM][SCN]) + alcohols} have been measured at temperatures from T = (298.15 to 308.15) K and pressures from p = (0.1 to 40) MPa. These results have been used to calculate the excess molar volumes, partial molar volumes, apparent molar volumes and partial molar volumes at infinite dilution. The experimental density data were correlated by using the Tait-Tammann equation to obtain isothermal compressibility and isobaric expansion. Moreover, the values of excess molar volume were used to test the applicability of the Extended Real Associated Solution Model (ERAS Model). In order to elucidate possible structural phenomena, spectroscopic properties (H-NMR, C-NMR and FT-IR) were combined with the thermodynamic results trying to understand the molecular interactions among the unlike components present in the studied systems.