In this study, the pervaporative dehydration of diethylene glycol (DEG) through a commercial hollow fiber membrane was investigated at various feed temperatures in the range of 333363 K with feeds containing 0.52.0 wt % water. Unlike the usual pervaporative dehydration process in which water is less volatile than the organic solvent, the feed mixture used in this study contained the organic component DEG, which is less volatile than water, resulting in unique permeation behaviors. The permeation behaviors of the individual components were investigated as functions of the feed temperature and feed composition. In particular, the effect of the low vapor pressure characteristics of DEG was investigated. Semi-empirical equations for predicting the individual component fluxes and separation factor were quantified directly from actual dehydration pervaporation of DEG. (c) 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013