Pervaporation may successfully be implemented for the separation of azeotropic mixtures which generally requires energy intensive separation procedures. Separation of methanol from methyl acetate by pervaporation is a representative application. In this study the commercial polyvinyl alcohol (PVA)-based membranes PERVAP(TM) 4155-30, PERVAP(TM) 4155-70, and PERVAP(TM) 4155-80 were used to recover methanol from binary methanol-methyl acetate mixtures. The separation performance was investigated for various operating parameters such as feed composition, feed temperature, and permeate pressure and discussed in terms of permeance and selectivity. An empirical model was developed to quantify the effect of membrane swelling on the permeate flux.