In the present work, experimental density (ρ) and speed of sound (u) data for the binary mixtures of benzyl alcohol with acetic acid, propionic acid, and n-butyric acid have been reported over the complete range of mole fraction at 298.15 K ≤ T ≤ 313.15 K. Excess volumes (VE), excess isentropic compressibilities (κsE), excess partial molar volumes ((Formula presented.)), and excess partial molar volumes at infinite dilution ((Formula presented.)) have been computed from the experimental data. The excess thermodynamic properties are found to be negative over the entire range of composition at the investigated temperatures. The temperature dependence of the excess thermodynamic properties has been investigated. All the excess functions are correlated with the Redlich-Kister equation. Further, attenuated total reflection Fourier transform infrared (ATR-FTIR) spectra for the studied binary solutions have been recorded at the equimolar composition to evaluate the extent of cross-association between component molecules through intermolecular hydrogen bonding. © 2020 Informa UK Limited, trading as Taylor & Francis Group.