In this paper, experimental values of densities, viscosities and refractive indices of acetonitrile + 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol and poly (ethylene glycol) 200 binary liquid mixtures were measured at temperatures of 293.15, 298.15 and 303.15 K and atmospheric pressure (0.1 MPa) over the whole composition range. From the experimental measurements, different thermophysical properties including the excess molar volume, partial molar volume, partial molar volume at infinite dilution, thermal expansion coefficient, excess thermal expansion coefficient, molar refraction, refractive index deviation and viscosity deviation were calculated. Interactions between molecules in the mixtures are discussed using the obtained thermodynamic results. Moreover, to report the adjustable parameters and determine the prediction and correlation accuracy, models including the Peng-Robinson, Redlich-Kister, Prigogine–Flory–Patterson, Rackett, Lorentz-Lorentz, Andrade and two parameters McAllister equations were applied.