Currently, Zn-based catalysts for electrochemical CO2 reduction reactions are limited by their moderate carbophilicity, resulting in low catalytic activity and CO selectivity. To this end, we selected 5-mercapto-1-methylimidazole, a small molecule that possesses the ability to both coordinate to Zn and interact with the intermediates, to modify electrochemically deposited Zn nanosheets. The interaction between them effectively enhances intermediate adsorption by lowering the Gibbs free energy, which leads to an increase of the Faraday efficiency to 1.9 times and the CO partial current density to 3.0 times that of the pristine sample (-1.0 V vs. RHE).