Vapor-liquid equilibrium (VLE) and surface tension (ST) for the hexane + ethanol + cyclopentyl methyl ether mixture have been measured and modeled. VLE determinations are carried out in a dynamic Guillespie type cell at the isobaric condition of 94 kPa, whereas the dependence of ST on concentration is measured in a maximum differential bubble pressure tensiometer at atmospheric pressure and 298.15 K.The thermodynamical consistent VLE data exhibit positive deviation from ideal behavior without ternary azeotropy and are well correlated by Redlich–Kister expansion and predicted by the binary nonrandom two-liquid, Wilson and universal quasichemical activity coefficient models. The ST data exhibit negative deviation from the linear behavior and are smoothed using the Myers-Scott expansion, showing no ternary aneotropic behavior.The experimental data of VLE and ST are accurately characterized by applying the square gradient theory to the Peng–Robinson Stryjek–Vera equation of state (EoS) appropriately extended to mixtures employing the modified Huron–Vidal mixing rule. This theoretical framework shows that experimental VLE and ST data can be fully predicted by only using binary contributions within a global average absolute deviation of 1.25% for VLE and 6.1% for ST. The theoretical approach also provides a route to explore the concentration distribution of species in the interfacial region, where it is possible to conclude that hexane exhibits both adsorption and desorption; ethanol displays strong positive adsorption whereas CPME does not exhibit surface activity.