ABSTRACT Developing practical anion exchange membrane water electrolysis (AEMWE) technology encounters great challenges in not only cell efficiency but also long‐term durability due to mechanical electrocatalyst detachment and electrochemical dissolution of active species, especially for the anodic oxygen evolution reaction (OER). Herein, a “two‐pronged” approach is proposed to construct organophosphorus‐protected NiFe layered double hydroxide catalysts on plasma‐modified substrate, serving as an efficient and robust anode for practical AEMWE. Mechanical tests combined with operando spectroscopies and theoretical calculations demonstrate that the plasma modification strengthens the catalyst–substrate adhesion, while the organophosphorus protection prevents Fe leaching and promotes reaction kinetics during OER. The resultant electrode delivers an ultralow overpotential of 276 mV at 1 A cm −2 , together with a remarkable stability at 0.5 A cm −2 over 500 h. Furthermore, assembling the optimized anode into an AEMWE device contributes to a minimized cell voltage of 1.70 V at 1 A cm −2 , which sustains durable green hydrogen production with an economical energy consumption of 4.16 kW h Nm −3 H 2 .