Novel sulfonated poly (fluorenyl ether ketone) with pendant quaternary ammonium groups (SPFEICA) was successfully synthesized by one-pot copolymerization of bis(4-fluoro-3-sulfophenyl)sulfone disodium salt, 4,4'-difluorobenzophenone, bisphenol fluorene and 2,2'-dimethylaminemethylene-9,9'-bis(4-hydroxyphenyl) fluorene (DABPF). The chemical structures were confirmed by FT-IR, and H-1 NMR. The thermal properties were fully investigated by TGA. The synthesized copolymers SPFEKAs are soluble in aprotic solvents, and can be cast into membranes on a glass plate from their N,N'-dimethylacetamide (DMAc) solution. A new kind of amphoteric ion exchange membrane (AIEM) was obtained by immersed SPFEICA into 1 M sulfuric acid. The proton conductivities of these membranes are comparable to the most reported sulfonated polymers under the same conditions. The permeability of vanadium ions in vanadium redox flow battery (VRB) was effectively suppressed by introducing quaternary ammonium groups for Donnan exclusion effect. AIEM-20% possess a only 4.4% vanadium ion permeability of Nafion 115. Cell performance tests showed that the VRB assembled with AIEM-20% shows the highest coulombic efficiency (CE) at the current density of 50 mA/cm(2), because of its lowest VO2+ permeability. In conclusion, these ionomers could be promising candidates for ion-exchange membranes for VRB applications. Copyright (C) 2014, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.