The vapour pressures of liquid hex-2-yne + methyl butyl ether (MBE) and hex-3-yne + dibutyl ether (DBE) binary mixtures and of the four pure components are measured by a static method in the temperature range from 263 to 354 K. The isoplethal T-P data are reported and correlated with the Antoine equation. Interpolated data are also reported. Excess molar Gibbs energies, G(E), are calculated for several constant temperatures, taking into account the vapour-phase imperfection in terms of the second 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-2-yne + MBE and hex-3-yne + DBE in the framework of the DISQUAC and modified UNIFAC (Do) models. (c) 2007 Elsevier B.V. All rights reserved.