Cu is considered to be an effective electrocatalyst in CO/CO 2 reduction reactions (CORR/CO 2 RR) because of its C-C coupling into C 2+ products, but it still remains a formidable challenge to rationally design Cu-based catalysts for highly selective CO/CO 2 reduction to C 2+ liquid products such as acetate. We here demonstrate that spraying atomically layered Cu atoms onto CeO 2 nanorods (Cu-CeO 2 ) can lead to a catalyst with an enhanced acetate selectivity in CORR. Owing to the existence of oxygen vacancies (O v ) in CeO 2 , the layer of Cu atoms at interface coordinates with Ce atoms in the form of Cu-Ce (O v ), as a result of strong interfacial synergy. The Cu-Ce (O v ) significantly promotes the adsorption and dissociation of H 2 O, which further couples with CO to selectively produce acetate as the dominant liquid product. In the current density range of 50-150 mA cm -2 , the Faradaic efficiencies (FEs) of acetate are over 50% with a maximum value of 62.4%. In particular, the turnover frequency of Cu-CeO 2 reaches 1477 h -1 , surpassing that of Cu nanoparticle-decorated CeO 2 nanorods, bare CeO 2 nanorods, as well as other existing Cu-based catalysts. This work advances the rational design of high-performance catalysts for CORR to highly value-added products, which may attract great interests in diverse fields including materials science, chemistry, and catalysis.