In the present study, the permeation behavior of methanol and methyl acetate in the pervaporation (PV) experiments are compared with those in vapor permeation (VP) experiments using a PVA-based composite membrane. Experiments have been carried out to study the selectivity and mass transport flux of the systems under varying operations conditions of feed temperature (40-60 degrees C) and feed methanol concentrations (2-34 wt%). The selected membrane was found to be methanol selective. Results show higher permeation flux but a similar separation factor for methanol in PV than in VP. For PV operation, the resulting separation factor at 60 degrees C shows a monotonous decrease (6.4-4.1) as the alcohol concentration in the feed mixture increases (2.3-34 wt%), whereas the total flux increases from 0.97 to 7.9 kg m(-2) h(-1). Based on the solution-diffusion theory, a mathematical model that describes satisfactorily the permeation fluxes of methanol and methyl acetate in both the PV and VP processes has been applied. The fluxes of both permeants can be explained by the solution-diffusion model with variable diffusion coefficients dependent on MeOH concentration in the membrane. Both PV and VP processes can be described with the same model but using different fitting parameters. (c) 2006 Elsevier B.V. All rights reserved.