Electrocatalytic　CO2　reduction　(ECO2R)　to　CO　provides　a　promising　strategy　for　mitigating　atmospheric　CO2　levels　in　the　atmosphere　while　generating　value-added　chemical　feedstocks　for　industrial　applications.　However,　the　widespread　implementation　of　ECO2R　remains　constrained　by　insufficient　activity　and　Faradaic　selectivity　of　current　catalysts　under　practical　operating　conditions.　We　here　develop　a　hybrid　material　of　Ag　nanoparticles　embedded　in　cyclodextrin　(AgNPs-CD)　with　abundant　surface　hydroxyl　groups,　which　functions　as　an　efficient　catalyst　for　ECO2R　to　CO,　delivering　both　high　activity　and　excellent　selectivity.　The　AgNPs-CD　achieves　an　exceptional　CO　Faradaic　efficiency　(FECO)　of　97.6　%　at　an　ultralow　potential　of　−0.4　V　vs.　RHE　and　sustains　high　FECO　values　ranging　from　93.5　%　to　99.8　%　over　a　broad　potential　window　(−0.4　to　−1.0　V　vs.　RHE),　while　simultaneously　affording　a　high　CO　partial　current　density　(JCO)　exceeding　200　mA　cm−2.　In　situ　electrochemical　spectroscopy　and　theoretical　calculations　reveal　that　AgNPs-CD　stabilizes　*COOH　with　a　lower　Gibbs　free　energy　and　inhabits　the　hydrogen　evolution　reaction　(HER)　with　high　energy　barrier,　making　high　activity　and　high　selectivity　toward　CO2　to　CO　conversion.　This　work　can　not　only　provide　an　efficient　strategy　to　enhance　the　performance　of　ECO2R　to　CO　but　also　shed　light　on　the　design　and　development　of　novel　electrocatalysts　with　low　overpotential　and　high　current　density.　©　2025　Elsevier　Inc.