The composite membranes with cellulose acetate (CA) as the separating layer material and polyacrylonitrile (PAN) as the supporting layer material were prepared for separating caprolactam (CPL) from CPL/water mixtures by pervaporation technique. The swelling experiments were carried out to investigate the effects of swelling time and CPL concentration on the degree of swelling. The results showed that the CA membrane reached swelling equilibrium within 24 h, and the degree of swelling first slightly decreased then increased with the increase of CPL concentration in the feed under the experimental conditions. Respectively comparing flux with permeance, and separation factor with selectivity, we found out that the separation performance of the CA/PAN composite membrane is more strongly dependent on its hydrophilic/hydrophobic nature as well as on the effects of operating parameters, such as feed composition concentration and feed temperature.