AbstractExcess volumes and adiabatic compressibility have been measured in several binary liquid mixtures to answer the question whether structural information can be gained through the analysis of the concentration dependence of the excess quantities. The obtained results are compared with independent indications from Raman spectroscopy, which is able to probe directly the occurrence and the nature of effective intermolecular interactions. Some doubts have arisen against the usual approach adopted for estimating the excess quantities and about the adequacy of the usual assumptions for the reference ideal behaviours. In particular, it is shown how excess compressibility can result just from statistical effects also in absence of any excess volume contribution. The leading idea is supported by the comparison of the experimental data with the results from a naive model for binary mixtures of hard spheres. The model turns out to be able to produce a very wide spectrum of structural and thermodynamic behaviours depending on the values of its parameters and on the nature (additive or non‐additive) of the hard‐sphere potential. A discussion is proposed on the re‐evaluation of excess thermodynamic data and on their ability in providing direct information on intermolecular interactions. Copyright © 2008 John Wiley & Sons, Ltd.