The discovery of materials for the electrochemical transformation of carbon dioxide into liquid fuels has the potential to impact large-scale storage of renewable energies and reduce carbon emissions. Here, we report the discovery of an electrocatalyst composed of gold nanoparticles on a polycrystalline copper foil (Au/Cu) that is highly active for CO2 reduction to alcohols. At low overpotentials, the Au/Cu electrocatalyst is over 100 times more selective for the formation of products containing C–C bonds versus methane or methanol, largely favouring the generation of alcohols over hydrocarbons. A combination of electrochemical testing and transport modelling supports the hypothesis that CO2 reduction on gold generates a high CO concentration on nearby copper, where CO is further reduced to alcohols such as ethanol and n-propanol under locally alkaline conditions. The bimetallic Au/Cu electrocatalyst exhibits synergistic activity and selectivity superior to gold, copper or AuCu alloys, and opens new possibilities for the development of CO2 reduction electrodes exploiting tandem catalysis mechanisms.