Abstract Developing cost‐effective, robust, and durable catalysts for water oxidation in acidic conditions remains a significant challenge for the practical application of proton exchange membrane electrolyzers. Cobalt‐based spinel catalysts, known for their effective oxygen evolution reaction (OER) activity in acidic environments, are promising alternatives to the costly iridium‐based catalysts. However, their application is often limited by poor stability under corrosive acidic conditions and oxidative potential. Here it is demonstrated that doping Co 2 MnO 4 with Ni effectively regulates the structural and electronic properties of the catalysts, enabling stable operation for over 285 h at 100 mA cm −2 in 0.5 m H 2 SO 4 . This stability enhancement is primarily due to the increased exposure of the (400) facet, a result supported by theoretical studies. The proton exchange membrane water electrolysis (PEMWE) performance of Ni(5%)Co 2 MnO 4 further demonstrates its potential, achieving 1 A cm − 2 at a cell voltage of 2.3 V, with minimal degradation over 100 h at 500 mA cm − 2 . This study not only provides insights into the design of advanced OER catalysts through the doping of heteroatoms but also offers a pathway to enhance the sustainability and economic viability of acidic OER applications.