In this paper, sodium alginate (SA) and chitosan (CS) were modified by copper phthalocyanine tetrasulfonic acid (CuTsPc) and copper tetraaminophthalocyanine (CuTAPc) respectively to prepare the CuTsPc-SA/mCS bipolar membrane (BPM) and the mSA/CuTAPc-CS BPM (here, mCS and mSA indicate the CS anion exchange layer and the SA cation exchange layer modified by glutaraldehyde and Fe(3+) as linking reagents, respectively). Experimental results showed that the ion exchange capacities and the ion transmigration rates of the CuTsPc-SA cation exchange membrane and the CuTAPc-CS anion exchange membrane were increased. In comparison with the mSA/mCS BPM modified by Fe(3+) or ferrocene, the membrane impedance and the IR drop of the CuTsPc-SA/mCS BPM or the mSA/CuTAPc-CS BPM decreased. The CuTsPc-SA/mCS BPM had the lowest cell voltage, which was only 5.6V at a higher current density of 120 mA cm(-2). When the concentration of CuTsPc or CuTAPc was 5.0 wt%, both of the CuTsPc-SA/mCS BPM and the mSA/CuTAPc-CS BPM were stable in the acid solution ([H(+)] <8 mol L(-1)). (C) 2010 Published by Elsevier B.V.