Operating conditions play a significant role in determining the separation performance of a pervaporation process, because they not only manipulate the driving forces to transport permeants but also affect the physicochemical properties of the pervaporation membrane itself. In this study, fundamental governing equations have been derived to correlate separation performance with system operation conditions and intrinsic separation characteristics of the pervaporation membrane. Polybenzimidazole/polyetherimide (PBI/PEI) dual-layer hollow fiber membranes were chosen to study the pervaporation dehydration of ethylene glycol (EG) under different testing protocols. The effects of operational parameters such as operation temperature, permeate pressure, feed composition and operation duration on performance indicators (flux and separation factor, permeance and selectivity) have been investigated. Experimental results show that an increase in operation temperature results in an increase in flux and selectivity, but a decrease in permeance and separation factor. In addition to other factors, decreasing sorption, less EG-water clusters and lower membrane-EG affinity with increasing temperature, play essential roles for the opposite trends. Both flux and permeance decrease with an increase in permeate pressure, while both separation factor and selectivity have an up-and-down trend. An increase in EG composition in the feed from 50 to 90 wt.% results in a lower water flux and permeance, but EG flux and permeance first increase and then decrease. This is due to the combined effect of water-induced membrane swelling and the formation of an EG boundary layer upon the membrane surface. The long-term test up to 33 days proves the membrane durability for EG dehydration. This work may provide useful insights to pervaporation fundamentals, system design and scale up for the EG dehydration. (C) 2011 Elsevier B.V. All rights reserved.