gamma-valerolactone (GVL) has been identified as a renewable, versatile, and nontoxic building block for the chemical industry. Although several protocols were published for its synthesis, so far only a few studies concerning the separation and purification of the product were reported. Some of the procedures involve alcohols or lead to the formation of binary mixtures of alcohols and GVL, therefore the separation is of utmost importance to produce GVL. Isobaric vaporliquid equilibria of three binary systems (methanol, ethanol, and 2-propanol) of gamma-valerolactone were measured using a vapor condensate and liquid circulation VLE still. The experimental data were correlated with Wilson and UNIQUAC activity coefficient models and the results were compared with UNIFAC model calculations. Both models were found suitable for representing the VLE data. The refractive indexes of all systems were determined in the whole concentration range at T = 293.2 and 298.2 K. Good agreements between experimental and calculated VLE data were obtained.