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Developing an effective catalyst to reduce carbon dioxide (CO 2) to value-added C 2+ products is a key challenge for CO 2 utilization. Here we report a core-shell copper with native oxide (Cu@Cu 2 O) catalyst featuring a thin native oxide layer on the surface grown under ambient conditions. The Cu(I) oxide species on Cu@Cu 2 O surface remained relatively stable against reduction under CO 2 electroreduction condition, and the synergism between surface Cu+ and Cu0 in Cu@Cu 2 O contributed to boosting its efficiency and selectivity toward C 2 products. This Cu@Cu 2 O catalyst achieved an excellent selectivity (∼50% at −1.0 V vs reversible hydrogen electrode) for C 2 (ethylene and ethanol) production. [ABSTRACT FROM AUTHOR]