Despite the promising potential of non-platinum group metal (non-PGM) electrocatalysts for hydrogen production in anion exchange membrane (AEM) electrolyzers, their practical implementation remains challenging. Herein, we demonstrate the synergistic effects of intrinsic and extrinsic engineering on the performance of CuCo oxide for AEM electrolyzer. Intrinsic improvement was achieved by replacing Cu with Co3O4 (P-CCO), resulting in superior catalytic activity for the oxygen evolution reaction (OER) compared to Co3O4 (P-CO). Extrinsic improvement was achieved by fabricating Z-CCO with a larger electrochemical surface area and improved OER catalytic activity by engineering the surface morphology of P-CCO using a metal-organic framework (MOF). The intrinsic and extrinsic improvements dramatically enhanced the performance of the AEM electrolyzer, with the AEM electrolyzer featuring the intrinsically improved Z-CCO displaying the highest energy efficiency.