Comb-shaped polysulfone anion exchange membranes (AEMs) containing various pendant alkyl side chains were synthesized and characterized. Ionic clusters aggregation is observed in transmission electron microscopy (TEM) image and small-angle X-ray scattering (SAXS). The comb-shaped quaternized ammonium polysulfone (Cx-QAPSU) membranes show enhanced dimensional stability and ultra-low membrane area resistance (R-m). Notably, the C16-QAPSU with 16 carbon atoms has the best hydrophilic-hydrophobic phase separation structure and lowest R-m of 2.5 Omega cm(2) despite low ion exchange capacity (IEC) of 1.55 mmol/g and swelling ratio of 5.3%. Moreover, comb-shaped AEMs show much higher tensile strength (TS) compared to QAPSU membrane under the same IEC level. The C16-QAPSU with lowest R-m of 2.5 Omega cm(2) exhibits the highest TS of 16.7 MPa. These results indicate that the long alkyl side chains especially the length of the pendant side chain of Cx-QAPSU up to C16 achieve an electrochemical-mechanical balance of AEMs. In electro-electrodialysis systems, the comb-shaped AEMs exhibit higher purification efficiency of wet phosphoric acid than non-comb-shaped AEMs.