Excess thermodynamic properties provide fundamental information on the intermolecular interactions in multicomponent fluid mixtures. However, very often only phase equilibria is used to test the accuracy of any theory or molecular model describing the solution thermodynamic behaviour. Although this approach is valid and often sufficient, some situations require stronger tests to determine whether a model and/or theory can provide a realistic description of a particular system. Excess properties estimation is a valuable test for this purpose because excess properties are very sensitive to the molecular model details. The goal of this work is to show how simple models, with a reduced number of molecular parameters, are able to predict accurately excess thermodynamic properties. We concentrate on binary mixtures formed by different models of flexible molecules. In particular, we focus on two general models: the fully-flexible tangentially bonded Lennard–Jones chains model described with the SAFT VR [J. Chem. Phys. 106 (1997) 4168] approach, and the united-atom model combined with Monte Carlo simulation, in both cases applied to the description of short chain alkane mixtures (from methane to propane). While the first model does not consider intramolecular interactions and the bond length equals the monomer size, the second one incorporates a more realistic description. Although the molecular models are relatively simple, they are able to describe most of the microscopic features of real chainlike molecules. The predictions obtained from SAFT-VR and simulation are compared with available experimental data, and the agreement is good for a wide range of thermodynamic conditions. In addition to the vapour–liquid equilibria, both theory and simulation are able to characterize the most relevant features of two important excess thermodynamic properties, excess volume and enthalpy.