Wei An, Mingcheng Zhang, Muhan Na, Xinyi Li, Xinyu Zhao, Xiyang Wang, Yongcun Zou, Xiao Liang, Xu Zou
ABSTRACT The operational instability of IrRu‐based anodes, particularly under the dynamic regimes inherent to renewable energy, remains a critical barrier to cost‐effective proton exchange membrane water electrolysis. Here, we address this challenge by designing hollandite‐structured IrRuO x nanocrystals (H‐IrRuO x ) via a low‐temperature phase‐transition synthesis. Distinct from the conventional rutile structure, the open hollandite framework stabilizes sub‐4‐valent metal sites within a unique coordination environment, which simultaneously enhances the oxygen evolution reaction activity and suppresses metal dissolution by mitigating overoxidation. When integrated into membrane electrode assemblies, the H‐IrRuO x catalyst layer demonstrates exceptional durability, operating stably at industrial current densities (1–2 A cm −2 ) with a minimal voltage decay rate of <4 µV h −1 over 3700 h. Crucially, under harsh dynamic cycling, it retains 96% of its initial activity after 36 000 cycles, outperforming conventional benchmarks. This structural engineering strategy provides a viable path to durable, cost‐effective hydrogen production under realistic conditions.