Abstract: Three side-chain-type poly(aryl piperidine) (PTTP) polymers with varied substituent configurations, namely p-PTTP, m-PTTP, and o-PTTP, were synthesized via superacid-catalyzed polymerization. In this synthesis, p-terphenyl and N-methyl-4-piperidinone served as the fundamental monomers, while 4-(trifluoromethyl)acetophenone (p-TFE), 3-(trifluoromethyl)acetophenone (m-TFE), and 2-(trifluoromethyl)acetophenone (o-TFE) were introduced individually as functional comonomers with different trifluoromethyl substitution positions. Subsequent quaternization with methyl iodide yielded a series of side-chain-type PTTP anion exchange membranes (AEMs), designated as p-QPTTP, m-QPTTP, and o-QPTTP, respectively. The resultant AEMs were systematically characterized in terms of chemical structure, mechanical performance, and ionic conductivity. The optimal membrane sample was further assembled and tested in an anion exchange membrane electrolyzer. Results indicate that precise regulation of the side-chain substitution position effectively optimizes the ion exchange capacity, water uptake, and swelling ratio of the as-prepared membranes. The self-aggregation behavior of hydrophobic trifluoromethyl-containing side chains induces the formation of distinct microphase-separated morphologies, which construct continuous and efficient ion transport channels within the membrane matrix. Notably, the meta-substituted m-QPTTP membrane delivers a superior OH⁻ conductivity of 172.5 mS/cm at 80 ℃. After long-term alkaline aging in 3 mol/L KOH solution at 80 ℃ for 2000 h, the membrane maintains a conductivity retention rate of 80.9%, verifying its outstanding alkaline stability. When operated in a 1 mol/L KOH electrolyte at 60 ℃ under a current density of 1.0 A/cm², the m-QPTTP-based electrolyzer achieves a low cell voltage of 1.65 V and exhibits robust long-term operational durability with stable electrolysis performance for more than 250 h.