Electrocatalytic CO₂ reduction is a promising way to mitigate the urgent energy and environmental issues, but how to increase the selectivity for desired product among multiple competing reaction pathways remains a bottleneck. Here, we demonstrate that engineering the gas–liquid–solid contact interface on the electrode surface could tailor the selectivity of CO₂ reduction and meanwhile suppress H₂ production through regulated reaction kinetics. Specifically, polytetrafluoroethylene (PTFE) was utilized to modify a Cu nanoarray electrode as an example, which is able to change the electrode surface from aerophobic to aerophilic state. The enriched nano-tunnels of the Cu nanoarray electrode can facilitate CO₂ transportation and pin gaseous products on the electrode surface. The latter is believed to be the reason that boosts the Faradaic efficiency of liquid products by 67% and limits the H₂ production to less than half of before. This interface engineering strategy also lowered H₂O (proton) affinity, therefore promoting CO and HCOOH production. Engineering the electrode contact interface controls the reaction kinetics and the selectivity of products, which should be inspiring for other electrochemical reactions.