Low-coordinated copper facilitates the *CHCO affinity at enhanced rectifying interface of Cu/CuO for efficient CO-to-multicarbon alcohols conversion.

The carbon-carbon coupling at the Cu/CuO Schottky interface has been widely recognized as a promising approach for electrocatalytic CO conversion into value-added alcohols. However, the limited selectivity of C alcohols persists due to the insufficient control over rectifying interface characteristics required for precise bonding of oxyhydrocarbons. Herein, we present an investigation into the manipulation of the coordination environment of Cu sites through an in-situ electrochemical reconstruction strategy, which indicates that the construction of low-coordinated Cu sites at the Cu/CuO interface facilitates the enhanced rectifying interfaces, and induces asymmetric electronic perturbation and faster electron exchange, thereby boosting C-C coupling and bonding oxyhydrocarbons towards the nucleophilic reaction process of *HCCO-CO. Impressively, the low-coordinated Cu sites at the Cu/CuO interface exhibit superior faradic efficiency of 64.15  ±  1.92% and energy efficiency of ~39.32% for C alcohols production, while maintaining stability for over 50 h (faradic efficiency >50%, total current density = 200 mA cm) in a flow-cell electrolyzer. Theoretical calculations, operando synchrotron radiation Fourier transform infrared spectroscopy, and Raman experiments decipher that the low-coordinated Cu sites at the Cu/CuO interface can enhance the coverage of *CO and adsorption of *CHCO and CHCHO, facilitating the formation of C alcohols.