This study presents a novel strategy for stable and efficient brine oxidation using CoFeAl-layered double hydroxide (CoFeAl-LDH) anodes. The CoFeAl-LDH anodes, synthesized via a one-step hydrothermal method, demonstrate exceptional oxygen evolution reaction (OER) activity and stability. The anodes are capable of operating continuously for 350 hours at 2 A cm⁻² in 6-fold concentrated seawater without corrosion. The key to this performance is the dissolution of Al³⁺ ions during the OER process, which creates M³⁺ vacancies that enhance OER activity. Additionally, self-originated Al(OH)ₙ⁻ species adsorb on the anode surface, improving stability by repelling Cl⁻ ions through Coulombic forces. The study highlights the self-protective properties of CoFeAl-LDH, which enable it to resist corrosion in the presence of high concentrations of Cl⁻. The anode's ability to adsorb OH⁻ ions and repel Cl⁻ ions is crucial for maintaining stability under harsh conditions. The CoFeAl-LDH anode was tested in real seawater with high Cl⁻ and Br⁻ concentrations, demonstrating its effectiveness in brine electrolysis. The anode was also integrated into a membrane electrode assembly (MEA), which operated continuously for 500 hours at 1 A cm⁻², showing its feasibility for practical applications. The study also provides structural characterizations of CoFeAl-LDH before and after activation, revealing the formation of Al³⁺ vacancies and the adsorption of Al(OH)ₙ⁻ species. These findings support the enhanced OER performance and stability of CoFeAl-LDH. The results indicate that the CoFeAl-LDH anode is a promising candidate for seawater electrolysis due to its high efficiency, stability, and resistance to corrosion. The study underscores the importance of understanding the role of Al³⁺ dissolution and Al(OH)ₙ⁻ adsorption in enhancing the performance of anodes in brine electrolysis.This study presents a novel strategy for stable and efficient brine oxidation using CoFeAl-layered double hydroxide (CoFeAl-LDH) anodes. The CoFeAl-LDH anodes, synthesized via a one-step hydrothermal method, demonstrate exceptional oxygen evolution reaction (OER) activity and stability. The anodes are capable of operating continuously for 350 hours at 2 A cm⁻² in 6-fold concentrated seawater without corrosion. The key to this performance is the dissolution of Al³⁺ ions during the OER process, which creates M³⁺ vacancies that enhance OER activity. Additionally, self-originated Al(OH)ₙ⁻ species adsorb on the anode surface, improving stability by repelling Cl⁻ ions through Coulombic forces. The study highlights the self-protective properties of CoFeAl-LDH, which enable it to resist corrosion in the presence of high concentrations of Cl⁻. The anode's ability to adsorb OH⁻ ions and repel Cl⁻ ions is crucial for maintaining stability under harsh conditions. The CoFeAl-LDH anode was tested in real seawater with high Cl⁻ and Br⁻ concentrations, demonstrating its effectiveness in brine electrolysis. The anode was also integrated into a membrane electrode assembly (MEA), which operated continuously for 500 hours at 1 A cm⁻², showing its feasibility for practical applications. The study also provides structural characterizations of CoFeAl-LDH before and after activation, revealing the formation of Al³⁺ vacancies and the adsorption of Al(OH)ₙ⁻ species. These findings support the enhanced OER performance and stability of CoFeAl-LDH. The results indicate that the CoFeAl-LDH anode is a promising candidate for seawater electrolysis due to its high efficiency, stability, and resistance to corrosion. The study underscores the importance of understanding the role of Al³⁺ dissolution and Al(OH)ₙ⁻ adsorption in enhancing the performance of anodes in brine electrolysis.