Novel experimental liquid–liquid equilibrium measurements were performed for three ternary systems containing γ-valerolactone + n-tetradecane + (butanoic acid or hexanoic acid or methyl myristate) at T = 298.15 K. The quantification of the coexisting phases was performed using an indirect method which relies on the variation of physical properties (density) along the binodal curve. The experimental data were successfully correlated by the nonrandom two-liquid and the universal quasichemical models.