The poly(tetraphenyl ether ketone sulfone)s (PTPEKSs) were synthesized from 1,2-bis(4-fluorobenzoyl)-3,4,5,6-tetraphenyl benzene (BFBTPB) and bis(4-fluorophenyl) sulfone with bis(4-hydroxydiphenyl) sulfone in sulfolane. The synthesis of poly(tetraphenyl phthalazine ether sulfone)s (PTPPESs) was carried out via an intramolecular ring-closure reaction of dibenzoylbenzene moiety with hydrazine monohydrate. The PTPPES-QAHs [poly(tetraphenyl phthalazine ether sulfone-quaternary ammonium hydroxide)]s were synthesized via chloromethylation of PTPPES, quaternization with trimethylamine, and followed by an anion exchange of tetra-quaternary ammonium chloride polymers with KOH. Different contents of quatemized unit in PTPPES-QAH (15, 20, 25 mol% of BFBTPB) were studied by FT-IR, H-1 NMR spectroscopy, and thermogravimetric analysis (TGA). Sorption experiments were conducted to observe the interaction of quatemized polymers with water. The ion exchange capacity (IEC), ion conductivity and cell performance of PTPPES-QAH were evaluated with increasing the degree of quaternization. Copyright (C) 2012, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.