The continuous advancement in water electrolysis technologies has illuminated the potential of sustainable energy sources, particularly in the realm of green hydrogen production. Anion exchange membrane water electrolysis (AEMWE) stands out as a promising technology capable of theoretically yielding high-purity hydrogen. However, the commercialization of AEMWE faces challenges arising from the inherent discord between high performance and the elevated costs associated with noble metal catalysts, such as platinum and iridium. Moreover, prevalent studies often focus on a limited electrode area of less than 4 cm2, thereby restricting the exploitation of the high purity hydrogen production capabilities inherent in AEMWE. This research prioritizes the enhancement of performance through a meticulously crafted membrane-electrode assembly (MEA) employing a 25 cm2 Ni-frame caged NiMoO4 catalyst for cathode synthesis. The observed performance improvement is attributed to the augmented active site of the catalyst, consisting of NiMoO4 entrapped in the Ni substrate during the compression process of the electrode. Additionally, the increase in local pH at the interfacial between electrode and bulk electrolyte is facilitated by the capillary phenomenon resulting from the space between the Ni substrate and the NiMoO4 catalyst layer, leading to enhanced migration of the electrolyte containing hydroxide ions. Acknowledgements This research was supported by the Korea Institute of Energy Technology Evaluation and Planning (KETEP) granted financial resources from the Ministry of Trade, Industry & Energy, Republic of Korea (No. 20213030040590).