Poly(vinyl alcohol) (PVA) membranes (both homogeneous and asymmetric) were studied for the pervaporation separation of benzene/n-hexane and benzene/ cyclohexane mixtures. The asymmetric PVA membrane with skin and porous layers was prepared through the phase inversion technique. Both asymmetric and homogeneous membranes were benzene-selective for all the feed compositions. The benzene separation factor of homogeneous PVA membrane was smaller than three, and the total permeation flux was several g/m(2)/h. The benzene selectivity of the asymmetric PVA membrane was much higher than that of the homogeneous membrane; weight fraction of benzene in the permeate side was larger than 90% for all the feed compositions. On the other hand, the total flux was almost unchanged compared with that of the homogeneous membrane. These results indicate that the density of the skin layer of the asymmetric membrane should be much higher than that of the homogeneous membrane.