Electrochemical　carbon　dioxide　reduction　to　multi-carbon　(C2+)　products　presents　a　significant　opportunity　for　converting　greenhouse　gases　into　valuable　fuels　and　feedstocks.　The　development　of　highly　active　and　stable　catalysts　remains　a　critical　challenge.　In　this　study,　we　report　the　design　and　synthesis　of　cyclodextrin-modified　Cu/Cu2O　electrocatalysts,　which　exhibit　remarkable　efficiency　in　driving　the　CO2　electroreduction　process　towards　C2+　products.　Our　optimized　catalyst　achieves　a　C2+　Faradaic　efficiency　exceeding　50　%　at　a　high　current　density　of　over　200　mA　cm−2.　Experimental　findings,　supported　by　density　functional　theory　(DFT)　calculations,　reveal　that　cyclodextrin　plays　a　dual　role　in　stabilizing　Cu+　and　increasing　the　surface　density　of　hydroxyl　radicals.　This　dual　function　greatly　benefits　for　enhancing　*CO　intermediate　adsorption　and　promotes　*CHO　formation,　thereby　facilitating　the　crucial　dimerization　step　for　the　formation　of　C2+　products.　This　work　provides　valuable　insights　into　the　development　of　highly　active　and　selective　electrocatalysts　by　carefully　tuning　the　local　catalytic　environment,　potentially　opening　new　avenues　for　functionalizing　electrocatalysts　for　future　research　in　this　area.　©　2024　Elsevier　Inc.