Developing anion exchange membranes (AEMs) is an effective way to reduce the cost of water electrolyser systems and fuel cell systems because of the no requirement of platinum-group-metal (PGM) catalysts. However, low conductivity and poor stability are the bottlenecks that constrain its development. In this work, we propose a series of performance enhanced poly (terphenyl-co-fluorene quinuclidinium) (TPFQ) AEMs. The hydroxide conductivity of TPFQ-10 reached 178.5 mS cm−1 at 80 °C. The rigid fluorene group gives the membrane better dimensional stability (swelling ratio: 7.7% in pure water and 1.2% in 10 M NaOH at 80 °C for TPFQ-10). In particular, the membranes exhibit extremely high alkaline stability, with almost no conductivity loss over more than 2000 h in a 10 M NaOH solution. The AEM water electrolysers (AEMWEs) with nickel-alloy foam electrodes shows an excellent current density of 2.32 A cm−2 at 2.0 V. The AEMWEs can work steadily at a current density of 0.5 A cm−2 in 5 M NaOH at 80 °C for more than 500 h, with a low voltage rising rate of 56 μV h−1.