gamma-Valerolactone (GVL) has recently been considered as a suitable solvent for synthesis and catalysis. By the application of GVL in scaled-up processes, it can be mixed with various components, including commonly utilized polar aprotic solvents such as acetone and ethyl acetate. Herein, isobaric vapor-liquid equilibria (VLE) of acetone, ethyl acetate, and gamma-valerolactone were investigated at p = 101.3 kPa with a vapor liquid equilibrium. In addition, the VLE data series of GVL-water binary mixture was extended. The experimental data were correlated with Wilson, NRTL, and UNIQUAC activity coefficient models, whereas the results showed a greater difference to the UNIFAC model calculations. The refractive indexes of the mixture were also determined in the whole concentration range at T = 293.2 and 298.2 K.