LAUSR

Constructing Cu0–Cu+ double‐active sites is significant for C–C coupling to produce multicarbon products during the CO2 electrocatalytic reduction process. However, Cu‐based precursors (including Cu+) are easily reduced to Cu0, especially at large current densities. Thus, developing a facile Cu+ stabilization method to form Cu0–Cu+ double‐active sites is highly desirable but challenging. Herein, fullerene (C60) is used as an electronic buffer to stabilize the Cu+ site. Then, a composite of copper oxide and C60 precursor is designed to obtain a catalyst consisting of in situ formed Cu0–Cu+ double‐active sites. The catalyst not only delivers up to 61% multicarbon (C2+) products Faraday efficiency at a partial current density of 366 mA cm−2 but also exhibits a good 12 h durability of the Cu+ site at −1.4 V versus reversible hydrogen electrode. Moreover, the Cu0–Cu+ double‐active sites are revealed to induce the preferential coupling of *CO and *CHO over *CO dimerization, accounting for the enhanced C2+ selectivity.