A series of anion exchange membranes (AEM) based on block quaternary ammonium poly(arylene ether sulfone) (QA‐bPAES) were successfully synthesized from 9,9′‐bis(4‐hydroxyphenyl) fluorene, 4,4′‐(hexafluoroisopropylidene) diphenol and 4,4′‐difluorodiphenyl sulfone via block polymerization, chloromethylation, quaternization, alkalization and solution casting. Properties of the obtained QA‐bPAES membranes, including ion exchange capacity (IEC), water uptake, swelling ratios, methanol permeability and ion conductivity were investigated. The obtained QA‐bPAES membranes showed low water uptakes, high ion conductivities and good physical and chemical stability. For example, the membrane of QA‐bPAES(20/10)‐1.34 with IEC of 1.34 mmol g−1 exhibited swelling ratios of 5.0% and 5.1% in in‐plane and through‐plane direction, respectively, and ion conductivity of 15.6 mS cm−1 in water at 60 °C with low methanol permeability of 1.06 × 10−7 cm2 s−1 (25 °C). All the results indicated that this type of block membranes had good potentials for alkaline anion exchange membrane fuel cell applications.