Alkyl vinyl ethers such as methyl vinyl ether, propyl vinyl ether, isopropyl vinyl ether, butyl vinyl ether and isobutyl vinyl ether are usually used as industrial solvents and chemical intermediates in the chemical or pharmaceutical industry. Recently, they are popularly used as raw materials for polymer electrolyte membrane fuel cells and as cellulose dyeing assistants. However, very few investigations about process design and operation data were reported for alkyl vinyl ether compounds and there are no data for propyl vinyl ether(PVE) systems as far as we know. In this work, the isothermal VLE data are reported at 333.15 K for the ternary systems of {PVE + ethanol + benzene} by using headspace gas chromatography(HSGC) and these VLE data were correlated using Wilson, NRTL and UNIQUAC equations. The excess volumes(VE) and deviations in molar refractivity(ΔR) data are also reported for the sub binary systems {PVE + ethanol}, {ethanol + benzene} and {PVE + benzene} at 303.15 K. These data were correlated with Redlich-Kister equation. In addition, isoclines of VE and DR for ternary system {PVE + ethanol + benzene} were also calculated from Radojkovic equation.