Excess molar volumes of binary mixtures of toluene and ethylbenzene with propylbenzene, butylbenzene and hexylbenzene were determined at 298.15, 308.15 and 318.15 K (except for toluene + butylbenzene for which the excess molar volume was determined only at 298.15 K) using a vibrating tube densitimeter. The experimental excess molar volumes are compared with the calculated values based upon Flory’s theory of liquid mixtures.