The vapor pressures of liquid hex-1-yne or hex-2-yne + methyl 1, 1-dimethylethyl ether (MTBE) binary mixtures and of the three pure components were measured by a static method at several temperatures between 263 and 343 K. These data were correlated with the Antoine equation. Excess molar Gibbs energies G(E) were calculated for several constant temperatures, taking into account the vapor-phase imperfection in terms of the second molar virial coefficients, and were fitted to the Redlich-Kister equation. Calorimetric excess enthalpy H-E measurements, for these binary mixtures, are also reported at 298.15 K. The experimental VLE and H-E data were used, examining the binary mixtures hex-1-yne or hex-2-yne + MTBE in the framework of the DISQUAC and modified UNIFAC (Do) models. The DISQUAC calculations, reporting a new set of interaction parameters for the contact carbon-carbon triple bond/oxygen ether, is regarded as a preliminary approach. (c) 2006 Elsevier B.V. All rights reserved.