Experimental values of density and viscosity were measured for pure aniline, 2-propanol, 2-butanol, and 2-pentanol, along with their binary mixtures with aniline over the entire range of mole fraction at the temperatures 293.15−323.15 K. Excess molar volumes and viscosity deviation were calculated from the experimental data of density and viscosity and show negative values for all binary mixtures. Free-volume theory was coupled with the PC-SAFT model for calculation of viscosities of pure fluids and their binary mixtures. In all cases, this model is provided satisfactory performance, and the maximum of average absolute deviation is 2.38%.