Vapor-liquid equilibrium (VLE) data for the binary systems, 2-methylpentane + ethanol,and 2-methylpentane + 2-methyl-2-propanol (TBA), are reported at 101.3 kPa, including pure component vapor pressures. The systems deviate remarkably from ideal behaviour presenting one positive azeotrope. The activity coefficients and boiling points of the solutions were correlated with its composition by Wilson, UNIQUAC, NRTL, and Wisniak-Tamir equations.