The effects of interactions between permeant molecules or permeant and membrane material have been investigated on the permeation behavior of permeants in pervaporation of water/alcohol mix¬tures. A poly(vinyl alcohol) (PVA) membrane crosslinked with glutaraldehyde was employed in this study. A homologous series of alcohols in aqueous solution were used as feed. The pervaporation experiments were carried out with feed having 70-97 wt.% of alcohol contents and at various feed temperatures. In a high alcohol content above 92 wt.%, the permeation rate was increased in the order of interaction strength between alcohol and water in feed. However, in a low alcohol content below 90 wt.%, the tendency of the permeation rate was found to be opposite. These observations were discussed in terms of changes in interaction between permeant/permeant or permeant/membrane in varying feed composition and feed temperature.