Liquid-liquid equilibrium (LLE) data from 288.15 K to 323.15 K are reported for the binary system of propyl vinyl ether (PVE) + water, and tie-lines for the ternary systems of PVE + methanol or ethanol + water at 298.15 K were analytically determined by using a stirred and thermoregulated cell. The experimental data were correlated by using the NRTL equation. Additionally, the deviations in molar refractivity (Delta R) at 293.15 K for the binary systems of PVE + ethanol, ethanol + 2,2,4-trimethylpentane, and PVE + 2,2,4-trimethylpentane were measured, and the excess molar volumes (V-E) and Delta R for the ternary system of PVE + ethanol + 2,2,4-trimethylpentane were determined from the measured densities and refractive indices.