Anion exchange membrane (AEM) water electrolysis is a promising technology for hydrogen production from renewable energy sources. However, the bottle‐neck of its development is the poor comprehensive performance of AEM, especially the stability at high concentrated alkaline condition and temperature. Herein, we propose a new cationic group N‐methylquinuclidinium with enhanced alkaline stability and hereby a full‐carbon chain poly(aryl quinuclidinium) AEM was prepared. Compared with reported AEMs, it shows ultra‐high comprehensive alkaline stability (no chemical decomposition, no decay of conductivity) in 10 M NaOH aqueous solution at 80°C for more than 1800 h, excellent dimensional stability (swelling ratio: < 10% in pure water, < 2% in 10 M NaOH) in OH− form at 80°C, high OH− conductivity (∼139.1 mS/cm at 80°C) and high mechanical properties (tensile strength: 41.5 MPa, elongation at break: 50%). The water electrolyser using our AEM exhibits a high current density (1.94 A/cm2 at 2.0 V) when assembled with nickel‐alloy foam electrodes, and high durability when assembled with nickel foam electrodes.This article is protected by copyright. All rights reserved