To clarify the cause of time-dependent separation behavior, the pervaporation performance with operating time through pure poly(vinyl alcohol) (PVA) membrane and glutaraldehyde (GA) cross-linked PVA membranes was investigated. The results showed that the water concentration in the permeate for the air-side surface of the PVA membrane increased dramatically from 92.2 to 95.7% in about 110 min and then remained almost unchanged. However, the water selectivity for the glass-side surface did not change with operating time. Similar results were observed for the GA cross-linked PVA membranes. Furthermore, the contact angle of water on the air-side surfaces of those membranes decreased with the time of contact with the feed. These results revealed that this dynamic pervaporation process was mainly attributable to the reconstruction of hydroxyl groups at the air-side surfaces of PVA membranes in response to the change of their surrounding medium during pervaporation. The reconstruction at the glass-side surface of the membrane did not occur because of the preferential localization of hydroxyl groups at the interface between the membrane and the glass plate during film formation of PVA solution. The above conclusion was further confirmed by the following results. The water concentration in the permeate through PVA membranes with the air-side surface facing the feed reached equilibrium more quickly with increasing operation temperature or decreasing degree of cross-linking, which was consistent with the fact that the rate of surface reconstruction accelerated with the increase of temperature or the decrease of the degree of cross-linking. (c) 2006 Elsevier Inc. All rights reserved.