Composite membranes composed of an acrylic acid-acrylonitrile copolymer layer crosslinked by ethylene glycol diglycidyl ether and a porous alumina support were prepared and evaluated for the pervaporation separation of methanol (MeOH) from MeOH/methyl t-butyl ether (MTBE) mixtures. The permeation fluxes of both components decreases and separation factor increases with increasing crosslinking agent content. Moreover, the permeation rate is expressed by the solution-diffusion model, considering the swelling effect of methanol component, and the effect of temperature on the permeation fluxes and the separation factor is estimated by using the apparent activation energy values.