Accurate experimental data of vapor-liquid equilibria (VLE) and excess enthalpies are reported for four binary systems: (1-pentanol + 1-hexene), (2-pentanol + 1-hexene), (1-pentanol + 1,2,4trimethylbenzene) and (2-pentanol + 1,2,4-trimethylbenzene). An isothermal total pressure cell was used for measuring VLE at T=313.15 K. The data were fitted using Margules, Wilson and NRTL equations. Excess enthalpies were measured at two different temperatures T = (298.15 and 313.15) K using an isothermal flow calorimeter and were correlated by the Redlich-Kister equation. All systems present a positive deviation from the Raoult's Law. An azeotropic behavior with maximum pressure is observed for the mixtures 1-pentanol or 2-pentanol with 1,2,4-trimethylbenzene. In addition, an endothermic behavior, which increases with temperature, is obtained when the alcohols are mixed with these hydrocarbons. (C) 2018 Elsevier B.V. All rights reserved.