Electrochemical reduction of CO2 reaction (CO2RR) is recognized as a complicated process involving multiple steps on gas-electrode-solution interface. Hence, it is equally important to construct highly-efficient active sites and regulate favorable microenvironments around the reaction interface. Herein, we propose a biomimetic strategy to address both issues simultaneously in one catalytic system. We firstly evaporate isolated Au sites on the surface of the Cu layer to tune the intrinsic activity of Cu catalyst, then fix hexanethiol (HEX) molecules onto the Au sites through Au-S bonds to regulate reaction microenvironments (CuAu-HEX). Specifically, those Au/Cu bimetallic active sites can decrease the energy barriers for C-C coupling procedure and accelerate the generation of multi-carbon products. More importantly, those stable and non-dense HEX molecules on Au sites can ensure long-term hydrophobicity and high local concentration of CO2 around active sites, rather than block the channels for reactant transfer. Consequently, this unique structure is favorable for the pathways towards multi-carbon products, generating >
70% faraday efficiencies (FE) for multi-carbon products even at under ampere-level current densities. Intriguingly, this modification layer is very similar to animal hair follicles, which might present a new strategy to regulate the interfacial environments in various electrocatalytic reactions.