Liquid-liquid equilibrium (LLE) data for the ternary systems of propyl vinyl ether + C-3 or C-4 alcohols (1-propanol, 2-propanol, 1-butanol, and 2-butanol) + water at 298.15 K were analytically determined by using stirred and thermoregulated cells. Experimental LLE data were correlated with the NRTL and UNIQUAC equations. The distribution and selectivity Of C3 or C4 alcohols as a solvent were analyzed. Additionally, excess molar enthalpies at 303.15 K are reported for the binary systems of propyl vinyl ether + ethanol, ethanol + isooctane, and propyl vinyl ether + isooctane. These data were obtained by using an isothermal flow calorimeter. The isocline of excess molar enthalpies for the ternary system of propyl vinyl ether + ethanol + isooctane at 303.15 K was calculated using the Radojkovic equation.