Beyond Copper: Emerging Non‐Cu Catalysts for Multi‐Carbon Products in Electrochemical CO ₂ Reduction

The electrochemical CO 2 reduction reaction (CO 2 RR) to value‐added multi‐carbon (C 2+ ) products represents a promising pathway for establishing a sustainable carbon cycle. Copper (Cu)‐based catalysts are traditionally the most effective materials for C 2+ products formation, but their complex product distributions and poor stability limit practical applications. To this end, researchers have shifted their focus toward non‐Cu‐based systems, including Fe‐, Co‐, Ni‐, Sn‐based catalysts; other non‐Cu metal systems; molecular electrocatalysts, including MOFs and COFs; and metal‐free heteroatom‐doped carbon materials. Through precise structural design and modulation, these systems opened new routes for C─C coupling and improved C 2+ selectivity. Starting from C─C coupling mechanisms, this review systematically summarizes recent advances in non‐Cu catalysts for C 2+ product formation. It highlights their distinct reaction pathways and key intermediates relative to Cu‐based systems. Furthermore, strategies involving structural regulation, interface engineering, and multiscale computation for enhancing C 2+ product selectivity were highlighted. Finally, the key challenges and opportunities were also discussed. This review aimed to guide the rational design of efficient and durable non‐Cu catalytic systems for CO 2 RR.