AEMs with high ionic conductivity and excellent alkali stability are one of the cores to ensure that AEMWE achieves high performance. For the current problems of AEMs, multi-cation side chain crosslinkers present a mitigation strategy for the inherent “trade-off” between ion conductivity and mechanical strength and ensure exceptional alkali resistance. Herein, we introduced the first report on cross-linked AEMs with several hydrophilic multi-cation alkoxy chains, featuring ethylene oxide (EO). The differentiation in the hydrophilic/hydrophobic microphase separation structures, characterized by varying positions of the alkoxy chains within the three-stage multi-cation crosslinker, was explored by experiments and simulation, as well as bearing on the comprehensive performance of AEMs. Notably, EO located in the middle of multi-cations crosslinker was found to establish a coherent and ordered ion channel. QPTP-NOBN15 AEM exhibited the highest OH− conductivity (166.6 mS cm−1) and demonstrated lower water uptake (44.4 %) and swelling ratio (14.5 %) at 80°C. And meticulously designed cross-linked structures, along with ether-free backbones, bestowed upon QPTP-NOBN15 impressive alkali stability. After being retained in 1 M KOH solutions for 1200 h, ion conductivity of QPTP-NOBN15 remained largely unaffected. Furthermore, QPTP-NOBN15-MEA was evaluated by water electrolysis in 1 M KOH solutions at 60°C and found that the current density reached 1.8 A cm−2 at 2.99 V.

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