Anion exchange membrane water electrolysis (AEMWE) is a promising and potentially low-cost technology for producing green hydrogen, but a novel manufacturing technique with rational design of the electrodes is essential to improve the performance and stability. In this work, we investigate the effect of electrode structure on activity and the stability of AEMWEs by fabricating membrane electrode assemblies (MEAs). For the first time, the decal transfer method with platinum-group-metal-free (PGM-free) catalyst was successfully used in AEMWEs. With this method, deposition of a compact catalyst layer (CL) on the membrane was achieved without damaging neither the CL nor the membrane. The MEAs were designed for AEMWE using 1 M KOH as the electrolyte and the ionomer content was optimized for both cathode and anode. In the anode, a low ionomer loading improved activity and ionic conductivity, however, a higher ionomer content was beneficial for the cathode. Furthermore, the type of ionomer on the anode side has shown to be the major reason of loss of performance over time. An ionomer with low (1.4–1.7 meq g−1) Ion Exchange Capacity (IEC) and Nafion™ ionomer greatly improved the stability.