Abstract As the atmospheric carbon dioxide (CO2) level keeps hitting the new record, humanity is facing an ever‐daunting challenge to efficiently mitigate CO2 from the atmosphere. Though electrochemical CO2 reduction presents a promising pathway to convert CO2 to valuable fuels and chemicals, the general lack of suitable electrocatalysts with high activity and selectivity severely constrains this approach. Herein, a novel class of electrocatalysts is investigated, the quasi‐copper‐mers, in which the CuN4 rather than Cu atom itself serve as the basic building block. The respective quasi‐copper‐monomers, ‐dimers, and ‐trimers hosted in a graphene‐like substrate are first synthesized and then performed both experimental characterization and density functional theory (DFT) calculations to examine their atomic structures, evaluate their electrocatalytical performance and understand their underlying mechanisms. The experimental results show that the quasi‐copper‐trimers not only outperform the quasi‐copper‐dimer and quasi‐copper‐monomer when catalyzing CO2 to CO, it also shows a superior selectivity against the competing hydrogen evolution reaction (HER). The DFT calculations not only support the experimental observations, but also reveal the volcano curve and the physical origin for the qausi‐copper‐trimer superiority. The present work thus presents a new strategy in the design of high‐performance electrocatalysts with high activity and selectivity.
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