The electroreduction of carbon dioxide using renewable electricity is an appealing strategy for the sustainable synthesis of chemicals and fuels. Extensive research has focused on the production of ethylene, ethanol and n ‐propanol, but more complex C 4 molecules have been scarcely reported. Herein, we report the first direct electroreduction of CO 2 to 1‐butanol in alkaline electrolyte on Cu gas diffusion electrodes (Faradaic efficiency = 0.056%, j 1‐butanol = −0.080 mA cm −2 at −0.48 V vs. RHE) and elucidate its formation mechanism. Electrolyses of possible molecular intermediates, coupled with density functional theory, led us to propose that CO 2 first electroreduces to acetaldehyde—a key C 2 intermediate to 1‐butanol. Acetaldehyde then undergoes base‐catalyzed aldol condensation to give crotonaldehyde via electrochemical promotion from the catalyst surface. Crotonaldehyde is subsequently electroreduced to butanal, and then to 1‐butanol. In a broad context, our results point to the relevance of coupling chemical and electrochemical processes for the synthesis of higher molecular weight products from CO 2 .