Pervaporation of acetonitrile-water mixtures was carried out using three commercial membranes, viz: polydimethylsiloxane (PDMS), polytetrafluoroethylene (PTFE) and polyvinylidene fluoride (PVDF). The effects of feed concentration and feed temperature on the pervaporation performance, total and partial permeate fluxes, as well as acetonitrile selectivity, were investigated. It was found that increase in temperature yields higher total fluxes and lower selectivity for acetonitrile-water system. Changing concentration of acetonitrile in the range concerned leads to significant effect on total flux and selectivity. PDMS membrane was found to be most selective for acetonitrile separation. The total flux through the membranes was found to be in the order of PTFE > PVDF > PDMS, and the acetonitrile selectivity was found to be in the order of PDMS > PVDF > PTFE. The activation energies of water and acetonitrile associated with the permeation process for the PDMS, PTFE, and PVDF membranes were calculated to be in the ranges of 0.29-0.99, 0.6-0.87, 0.45-2.73 kJ/mol for acetonitrile and 1.23-1.95, 1.37-1.71, 1.16-3.37 kJ/mol for water at different concentrations, respectively.