Heat capacities for the binary mixtures of methanol with (C-1-C-4) alkylbenzoates and methylbenzoate with (C-1-C-11) alkan-1-ols have been measured over the whole composition range at 298.15 K under atmospheric pressure. From the experimental measurements, the derived excess molar heat capacities and partial excess molar heat capacities at infinite dilution have been calculated. A Redlich-Kister-type equation was fitted to these data, and the fitting parameters and standard deviations have been evaluated. Likewise, the IR spectra for the same systems have been recorded as a function of composition. The sets of experimental data gathered contribute to shed light onto the solvent structure and the underlying molecular interactions between the mixture constituents. The conclusions drawn have been established in terms of solute solvent and solvent solvent interactions and the ensuing structural effects between the solvent constituents.