For the purpose of separating alcohol–water mixtures by the use of the pervaporation technique, new composite membranes composed of polyion complexes (PIC) as a separating layer were developed. The polyion complex structure, consisting of polyacrylic acid (PAA) and polycation, provided excellent permeation rate and selectivity. Among the polycations, ionenes, which have quaternary ammonium groups in the backbone chain, were effective in giving membranes of higher permselectivities. High selectivity of PIC membranes was observed at high ethanol concentration regions in the feed mixture. For the azeotropic mixture of water/ethanol (95 wt % EtOH) at 60°C, the PAA-based PIC membrane had the following separation properties: separation factor ∼ 3,500 and permeation rate ∼ 1.6 kg/m2 h.