Density and speed of sound for binary systems of diethanolamine (DEA), triethanolamine (TEA), butylamine (BUT) and hexylamine (HEX) in aniline (ANL) were measured at temperature ranges of (303.15–318.15) K. From the measured experimental data, excess molar volume, VmE and deviation in isentropic compressibility, ∆kS were calculated. Excess molar enthalpy HmE was also calculated for the above mentioned systems at 303.15 K only. The values of VmE and HmE were negative for all systems in the whole composition range. The results were analyzed to discuss the effect of the alkyl chain length, the orientation and number of the OH groups and the structural deformation of the molecules in the face of unlike molecules. The values of VmE, ∆kS and HmE were correlated by Redlich ̶ Kister polynomial equation. The obtained values were used to evaluate the nature and type of intermolecular interaction in multicomponent mixtures. The experimental excess molar enthalpy data have been correlated with two thermodynamics models Wilson and NRTL. Theoretical calculations were also performed using the ab initio method to validate the data in which the associated molecular interactions were compared and discussed. The agreement between theoretical and experimental data was acceptable for all studied systems.