Latex membranes have recently been investigated for their application in pervaporation separation processes. Acrylonitrile-butyl acrylate copolymer latex membrane showed selective permeation to water in pervaporation with water-ethanol mixtures. Different from solvent-cast membranes, the pervaporation properties of latex membranes were found to change with the membrane aging time or under different aging conditions. It is shown that aging leads to better membrane fusion, thus decreasing the permeation rate and increasing the separation factor. Aging the membrane in a medium which keeps the latex particle from good fusion would cause a high permeation rate but a low separation factor. Based on our observations, a comprehensive transport mechanism of the permeant through latex membranes during pervaporation is proposed.