The separation of aqueous alcohol mixtures was carried out by use of a series of novel aromatic polyamide membranes. The aromatic polyamides were prepared by the direct polycondensation of 2,2'-dimethyl-4,4'-bis(aminophenoxyl)biphenyl (DBAPB) with various aromatic diacids, such as terephthalic acid (TPAc), 5-tert-butylisophthalic acid (TBPAc), and 4,4'-hexafluoroisopropylidenedibenzoic acid (FDAc). The pervaporation and evapomeation performance of these novel aromatic polyamide membranes for dehydrating aqueous alcohol solution were investigated. The solubility of ethanol in the aromatic polyamide membranes is higher than that of water, but the diffusivity of water through the membrane is higher than that of ethanol. The effect of diffusion selectivity on the membrane separation performances plays an important role in the evapomeation process. Compared with pervaporation, evapomeation effectively increases the permselectivity of water. Moreover, the effect of aromatic diacids on the polymer chain packing density, pervaporation, and evapomeation performance were investigated. It was found that the permeation rate could be increased by introduction of a bulky group into the polymer backbone. (C) 2003 Wiley Periodicals, Inc.