Vapor-liquid equilibria at 101.3 kPa have been determined for the binary systems methyl acetate + l-hexene and l-hexene + 2-propanol. The binary system methyl acetate + l-hexene exhibits positive deviations from ideal behavior and an azeotrope that boils at 325.38 K and contains 39.1 mol % l-hexene. The binary system l-hexene + 2-propanol presents strong deviations from ideality and an azeotrope that boils at 331.67 K and contains 79.60 mol % l-hexene. The activity coefficients and boiling point of the solution were correlated with its composition by the Redlich-Kister, Wohl, Wilson, UNIQUAC, NRTL, and Wisniak-Tamir equations.