Thermophysical properties of the hexane + 1-chlorohexane (or hexanoic acid or diisopropylether) + methylbenzoate ternary systems and their binary constituents are reported at 298.15 K and 0.1 MPa over the whole composition range. The properties and the optimized geometry of the gas-phase components were appraised from the density functional theory. To find out the causal link between the thermophysical measurements and the molecular level features, the derived mixing and excess functions of the ternary systems were looked into according to the scaled particle and Kirkwood-Buff analyses. The hydrogen bonding and dipole interactions along with the geometry effects brought about by the very different size and shape of the components give rise to complex mixed structures. Application of semiempirical models and use of simple cubic equations of state combined with a one-parameter van der Waals mixing rule has led to prediction of the ternary properties with variable degree of precision.