The variation in the morphology and electronic structure of copper during the electroreduction of CO₂ into valuable hydrocarbons and alcohols was revealed by combining in situ surface- and bulk-sensitive X-ray spectroscopies with electrochemical scanning electron microscopy. These experiments proved that the electrified interface surface and near-surface are dominated by reduced copper. The selectivity to the formation of the key C-C bond is enhanced at higher cathodic potentials as a consequence of increased copper metallicity. In addition, the reduction of the copper oxide electrode and oxygen loss in the lattice reconstructs the electrode to yield a rougher surface with more uncoordinated sites, which controls the dissociation barrier of water and CO₂. Thus, according to these results, copper oxide species can only be stabilized kinetically under CO₂ reduction reaction conditions.