With the urging development of a green and sustainable society, a cleaner energy carrier to substitute current fossil fuels is demanded. Hydrogen is a promising candidate due to its high energy content and innocuous combustion products. To produce hydrogen, water splitting technology, especially the proton-exchange membrane water electrolysis (PEMWE), has attracted intensive attention as the only by-product is oxygen. However, the anodic catalysts and porous transport layers suffer from severe corrosion caused by the strong acid local reaction environment, leading to performance degradation. Based on steel-based bulk electrodes, we observed a competition between corrosive dissolution and catalytic oxygen evolution above the water splitting potential. Steels with different compositions and surface modifications have been studied to reveal the effect of surface reconstruction on the catalytic active sites. As the oxygen is released from the metal oxides during the oxygen evolution reaction (OER), long-term stability or consistent regeneration of the corresponding oxides are vital. With increasing stability of the surface oxides, the proportion of catalytic current is improved, achieving higher Faradaic efficiency and less ion leaching. Multi-layer metal oxides on the surface of electrodes not only protect the matrix from strong acidic environment, but also provide catalytic activity for OER. Through this work, we expect to provide a possible pathway for the design of cheaper non-noble-metal-based catalysts and more affordable components in PEMWE.