The electrochemical carbon dioxide reduction reaction (CO 2 RR) to generate feedstocks for chemical products (e.g., carbon monoxide, CO) offers a highly attractive method for achieving the closure of the carbon cycle. Ionic liquids (ILs)functionalized Cu-based catalyst Cu 2 O-HKUST-1/IL 1 /PTFE was developed, configuring metal-organic frameworks(MOFs) based materials with high adsorption and multiple active sites. The modified electrocatalysts exhibited high specific surface area, strong CO 2 adsorption capacity, abundant active sites, and fast charge transfer rate. The nucleophilic active site of deprotonation at the C 2 site in imidazole ILs further improved the selectivity of proton migration and CO product generation, which was verified through DFT calculations for the low Gibbs free energy of the generated intermediate interactions. In addition, the hydrophobic interface constructed by PTFE facilitated the inhibition of the hydrogen evolution reaction (HER) and significantly improved the efficiency of CO 2 electroreduction. The Cu 2 O-HKUST-1/IL 1 /PTFE catalyst manifested a high C 1 Faraday efficiency (FE) up to 96.5% and in particular 92.7% for FE CO at −1.7 V vs RHE. The present work provides an efficient strategy for configuring ILs-functionalized MOFs-based materials with good hydrophobic interfaces to enhance the efficiency of CO 2 electroreduction to C 1 products.