Electrochemical reduction of CO₂ (CO₂RR) to multi-carbon products is a promising technology to store intermittent renewable electricity into high-added-value chemicals and close the carbon cycle. Its industrial scalability requires electrocatalysts to be highly selective to certain products, such as ethylene or ethanol. However, a substantial knowledge gap prevents the design of tailor-made materials, as the properties ruling the catalyst selectivity remain elusive. Here we combined in situ surface-enhanced Raman spectroscopy and density functional theory on Cu electrocatalysts to unveil the reaction scheme for CO₂RR to C₂₊ products. Ethylene generation occurs when *OC–CO(H) dimers form via CO coupling on undercoordinated Cu sites. The ethanol route opens up only in the presence of highly compressed and distorted Cu domains with deep s-band states via the crucial intermediate *OCHCH₂. By identifying and tracking the critical intermediates and specific active sites, our work provides guidelines to selectively decouple ethylene and ethanol production on rationally designed catalysts.