In this article, the pervaporation selectivity as a function of the membrane thickness is studied for the dehydration of acetic acid. From this study, it appeared that the selectivity of polysulfone (PSF), poly(vinyl chloride) (PVC), and polyacrylonitrile (PAN) decreases with decreasing membrane thickness, below a limiting value of about 15 m. However, in the case of gas separation, the selectivity of PSF membranes is independent of the membrane thickness. This phenomenon could not be explained by a difference in membrane morphology, sorption resistance, thermodynamic interaction, or coupling. It is believed that the decrease in selectivity for thin membranes has to be attributed to defects induced during pervaporation. These defects, crazes (and cracks), result from a reduced value of the critical strain, due to sorption of acetic acid/water and stresses between the polymer chains, due to a concentration gradient across the membrane.