Experimental data of excess enthalpies and vapour-liquid equilibria (VLE) are reported for the binary systems (1-pentanol n-hexane) and (2-pentanol + n-hexane). An isothermal flow calorimeter was used to determine excess enthalpies at T = (298.15 and 313.15) K and the results were fitted using Redlich-Kister equation. Vapour-liquid equilibria data were measured using an isothermal total pressure cell at T = 313.15 K. Barker's method allows to correlate these data using Margules, Wilson, NRTL and UNIQUAC equations. An endothermic behavior is observed when 1-pentanol or 2-pentanol is mixed with n-hexane whose effect increases at higher temperatures and both systems present a positive deviation from the Raoult's law. (C) 2016 Elsevier B.V. All rights reserved.