AbstractNon‐iridium acid‐stabilized electrocatalysts for oxygen evolution reaction (OER) are crucial to reducing the cost of proton exchange membrane water electrolyzers (PEMWEs). Here, we report a strategy to modulate the stability of RuO2 by doping boron (B) atoms, leading to the preparation of a RuO2 catalyst with long‐range disorder (LD‐B/RuO2). The structure of long‐range disorder endowed LD‐B/RuO2 with a low overpotential of 175 mV and an ultra‐long stability, which can maintain OER for about 1.6 months at 10 mA cm−2 current density in 0.5 M H2SO4 with almost invariable performance. More importantly, a PEM electrolyzer using LD‐B/RuO2 as the anode demonstrated excellent performance, reaching 1000 mA cm−2 at 1.63 V with durability exceeding 300 h at 250 mA cm−2 current density. The introduction of B atoms induced the formation of a long‐range disordered structure and symmetry‐breaking B−Ru−O motifs, which enabled the catalyst structure to a certain toughness while simultaneously inducing the redistribution of electrons on the active center Ru, which jointly promoted and guaranteed the activity and long‐term stability of LD‐B/RuO2. This study provides a strategy to prepare long‐range disordered RuO2 acidic OER catalysts with high stability using B‐doping to perturb crystallinity, which opens potential possibilities for non‐iridium‐based PEMWE applications.