In this study using poly(vinylalcohol) (PVOH) membranes cross-linked with tartaric acid (Tac) desorption experiments were performed for selected concentrations of binary ethyl acetate (EtAc)-water mixture at temperatures of 30 degrees, 40 degrees, and 50 degrees C to determine sorption of components. Sorption values measured were compared with those estimated by the Flory-Huggins approach. Additionally, desorption results were compared with pervaporation results of another study in terms of solution-diffusion theory, and the effect of thermodynamic interactions on selective transport of the binary mixture and membrane system was investigated. The results obtained show that selective transport of EtAc-water mixture was influenced by increasing temperature and water content in the feed. It is shown that preferential sorption is more effective for pervaporation selectivity than diffusion selectivity.