To address the insufficient ion conductivity of hydroxide exchange membranes (HEMs) used in alkali membrane fuel cells (AMFCs), we present a series of aligned layered double hydroxide (LDH)/polyphenyl ether (PPO) composite membranes based on the electrorheological effect. The hexagonal LDH was functionalized with N-spirocyclic ammonium (ASU-LDH) to enhance the electrorheological effect of the ASU-LDH as well as improve the ion conductivity of the ASU-LDH. The aligned ASU-LDH/triple-cation-functionalized PPO (ASU-LDH/TC-PPO) composite membranes were prepared by applied-electric field. The effective electric-induced ion channels (EICs) were constructed by aligned ASU-LDH nanosheets in HEMs, which are distinctly observed by scanning electron microscope (SEM). Notably, these EICs-contained ASU-LDH/TC-PPO composite membranes exhibit the higher ion conductivity and alkaline stability than those of normal TC-PPO and ASU-LDH/TC-PPO membranes. It is worth noticing that these EICs are different with the traditional phase-induced ion channels, the EICs show the shorter ion transport distances and broader water channels in HEMs. Attributing to EICs, the longitudinal ion conductivity of aligned ASU-LDH/TC-PPO membrane shows 32.2% and 18.7% improvement compared to pristine TC-PPO and normal ASU-LDH/TC-PPO membrane. The maximum ion conductivity of the aligned ASU-LDH/TC-PPO composite membrane reaches to 109.8 mS/cm at 80 degrees C. The long-term stability test shows that the aligned ASU-LDH/TC-PPO membranes still exhibit enhancing alkali resistance (83.2%) in 1 M KOH at 80 degrees C for 500 h. In brief, this work provides a novel and effective approach to prepare high-performance HEMs. (C) 2019 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.