The structure of the alkyl benzoate + n-alkane, and + alkan-l-ol binary mixtures were analyzed according to the Kirkwood-Buff fluctuation theory on the basis of both the mixture properties measured over a wide temperature range and the activity coefficients calculated with the modified UNIFAC (Dortmund) model as well. Application of this model reveals that both the microheterogeneous structure and the clustering effects are strongly dependent on the chain length of the n-alkane and alkan-l-ol cosolvents. Knowledge of the local composition around each type of molecule is drawn from the Kirkwood-Buff integrals and the excess (or deficit) molecules aggregated around a central one. The rather high values of the integrals evaluated for some of these systems provide first-hand evidence for phase splitting. The conclusions drawn support previous analyses and confirm the adequacy of the methodology put forward for studying liquid mixtures at microscopic level; easily measurable experimental properties can advantageously be used with the fluctuation theory.