The conversion of carbon dioxide to value-added products using renewable electricity would potentially help to address current climate concerns. The electrochemical reduction of carbon dioxide to propylene, a critical feedstock, requires multiple C-C coupling steps with the transfer of 18 electrons per propylene molecule, and hence is kinetically sluggish. Here we present the electrosynthesis of propylene from carbon dioxide on copper nanocrystals with a peak geometric current density of -5.5 mA cm(-2). The metallic copper nanocrystals formed from CuCl precursor present preponderant Cu(100) and Cu(111) facets, likely to favour the adsorption of key *C-1 and *C-2 intermediates. Strikingly, the production rate of propylene drops substantially when carbon monoxide is used as the reactant. From the electrochemical reduction of isotope-labelled carbon dioxide mixed with carbon monoxide, we infer that the key step for propylene formation is probably the coupling between adsorbed/molecular carbon dioxide or carboxyl with the *C-2 intermediates that are involved in the ethylene pathway.