Electrocatalytic reduction of CO2 recently emerged as a viable solution in view of changing the common belief and considering carbon dioxide as a valuable reactant instead of a waste product. In this view, we herein propose the one-step synthesis of gold nanostructures of different morphologies grown on fluorine-doped tin oxide electrodes by means of pulsed-laser deposition. The resulting cathodes are able to produce syngas mixtures of different compositions at overpotentials as low as 0.31 V in CO2-presaturated aqueous media. Insights into the correlation between the structural features/morphology of the cathodes and their catalytic activity are also provided, confirming recent reports on the remarkable sensitivity toward CO production for gold electrodes exposing undercoordinated sites and facets.