The study explores the use of high-entropy alloys (HEAs) as efficient and durable electrocatalysts for lithium-mediated CO₂ redox reactions. HEAs, characterized by their tunable geometric and electronic structures, are designed with an average diameter of 2.17 nm, containing Ni, Fe, Co, Cu, and Ru. These alloys exhibit significant charge redistribution due to the electronegativity-dependent nature of the elements, leading to the formation of active clusters of Ru, Co, and Ni. This results in lower energy barriers and stabilization of intermediates, enhancing the efficiency of both CO₂ reduction and LiCo₃ decomposition over extended periods. The NiFeCoCuRu HEA30/KB catalyst demonstrates a low overpotential of 0.82 V and excellent stability, outperforming pure Ru and other noble metal-based catalysts. The research provides insights into the active site interactions and the origin of the exceptional performance of HEAs in complex CO₂ redox reactions.The study explores the use of high-entropy alloys (HEAs) as efficient and durable electrocatalysts for lithium-mediated CO₂ redox reactions. HEAs, characterized by their tunable geometric and electronic structures, are designed with an average diameter of 2.17 nm, containing Ni, Fe, Co, Cu, and Ru. These alloys exhibit significant charge redistribution due to the electronegativity-dependent nature of the elements, leading to the formation of active clusters of Ru, Co, and Ni. This results in lower energy barriers and stabilization of intermediates, enhancing the efficiency of both CO₂ reduction and LiCo₃ decomposition over extended periods. The NiFeCoCuRu HEA30/KB catalyst demonstrates a low overpotential of 0.82 V and excellent stability, outperforming pure Ru and other noble metal-based catalysts. The research provides insights into the active site interactions and the origin of the exceptional performance of HEAs in complex CO₂ redox reactions.