The purpose of this article was to develop new membranes with a high selectivity and permeation rate for separation of an alcohol/water system. Crosslinked alginate composite membranes were prepared by casting an aqueous solution of alginate and 1,6-hexanediamine (HDM) onto a hydrolyzed microporous polyacrylonitrile (PAN) membrane. The influence of hydrolysis of the support membrane and crosslinking agent content in a dense layer on the selectivity and flux was studied and it was shown that both could improve the separation performance of the composite membrane greatly. The countercation of alginate coatings as a dense separating layer also influenced the separation properties of the membrane, which was better for K+ than for Na+. This novel composite membrane with K+ as a counterion has a high separation factor of 891 and a good permeation rate of 591 g m(-2) h(-1) for pervaporation of a 90 wt % ethanol aqueous solution at 70 degrees C. At the same time, SEM micrographs showed that the pore structure of the PAN microporous membrane is changed by hydrolysis. The reason for the influence of the preparation conditions on the separation performance of the novel membrane is discussed.