This work contributes to an improved understanding of the structure and dynamics of ester-containing solvents. A broad experimental study has been performed on the thermophysical properties of (C-6-C-14) n-alkane + (C-1-C-4) alkylbenzoate binary solvents over the whole composition range and within the 278.15-318.15 K temperature range. The excess and mixing derived properties were analyzed in terms of structural effects and intermolecular forces. To put forward reliable models that may describe the behavior of these complex mixtures, the cubic equations of state by Soave and Peng-Robinson were combined with a set of 10 different mixing rules to correlate the volumetric and viscometric properties. Likewise, to gain a deeper insight into the structure of these solvents the Prigogine-Flory-Patterson and extended real associated solution models were applied to correlate the excess molar volumes. The different contributions to the excess and mixing properties were analyzed as well as their variation with the nature and size of the components involved.