Electrochemical CO2 reduction reaction (eCO2RR) to value‐added multicarbon (C2+) products offers a promising approach for achieving carbon neutrality and storing intermittent renewable energy. Copper (Cu)‐based electrocatalysts generally play the predominant role in this process. Yet recently, more and more non‐Cu materials have demonstrated the capability to convert CO2 into C2+, which provides impressive production efficiency even exceeding those on Cu, and a wider variety of C2+ compounds not achievable with Cu counterparts. This motivates us to organize the present review to make a timely and tutorial summary of recent progresses on developing non‐Cu based catalysts for CO2‐to‐C2+. We begin by elucidating the reaction pathways for C2+ formation, with an emphasis on the unique C‐C coupling mechanisms in non‐Cu electrocatalysts. Subsequently, we summarize the typical C2+‐involved non‐Cu catalysts, including ds‐, d‐ and p‐block metals, as well as metal‐free materials, presenting the state‐of‐the‐art design strategies to enhance C2+ efficiency. The system upgrading to promote C2+ productivity on non‐Cu electrodes covering microbial electrosynthesis, electrolyte engineering, regulation of operational conditions, and synergistic co‐electrolysis, is highlighted as well. Our review concludes with an exploration of the challenges and future opportunities in this rapidly evolving field.