The Front Cover shows carbon dioxide reduction reaction (CO2RR) to C2 (e.g., ethylene, ethanol) driven by aminothiolate self-assembled monolayer (SAM)-modulated copper (Cu) catalysts. In their Communication, M. Wan et al. demonstrated that aminothiolate SAM-modulated Cu catalyst could improve the activity and selectivity of CO2RR-to-C2 using DFT calculations. The amine group of SAM provides an organic active site to facilitate CO2RR rate-limiting steps, i.e., CO2 initial activation and carbon-carbon coupling. The confined space effect induced by the high surface coverage of SAM tunes the binding energy of the key intermediate CO* on the inorganic Cu site, enlarges the binding energy difference between CO* and COH*, and consequently, further promotes carbon-carbon coupling. This theoretical work guides a novel catalyst design that provides hybrid organic-inorganic active sites, confinement effects and localized electric fields, and enables efficient CO2RR-to-C2. More information can be found in the Communication by M. Wan et al.