AbstractCu‐based electrocatalysts exhibit enormous potential for electrochemical CO2 conversion to added‐value products. However, high selectivity, specially toward C2+ products, remains a critical challenge for its implementation in commercial applications. Herein, the study reports the preparation of a series of electrocatalysts based on octadecyl amine (ODA) coated Cu2O nanoparticles (NPs). HRTEM images show ODA coatings with thickness from 1.2 to 4 nm. DFT calculations predict that at low surface coverage, ODA tends to lay on the Cu2O surface, leaving hydrophilic regions. Oppositely, at high surface coverage, the ODA molecules are densely packed, being detrimental for both mass and charge transfer. These changes in ODA molecular arrangement explain differences in product selectivity. In situ Raman spectroscopy has revealed that the optimum ODA thickness contributes to the stabilization of key intermediates in the formation of C2+ products, especially ethanol. Electrochemical impedance spectroscopy and pulse voltammetry measurements confirm that the thicker ODA shells increase charge transfer resistance, while the lowest ODA content promotes faster intermediate desorption rates. At the optimum thickness, the intermediates desorption rates are the slowest, in agreement with the maximum concentration of intermediates observed by in situ Raman spectroscopy, thereby resulting in a Faradaic efficiency to ethanol and ethylene over 73%.