The　selectivity　of　multicarbon　products　in　the　CO2　reduction　reaction　(CO2RR)　depends　on　the　spin　alignment　of　neighboring　active　sites,　which　requires　a　spin　catalyst　that　facilitates　electron　transfer　with　antiparallel　spins　for　enhanced　C−C　coupling.　Here,　we　design　a　radical-contained　spin　catalyst　(TEMPOL@HKUST-1)　to　enhance　CO2-to-ethylene　conversion,　in　which　spin-disordered　(SDO)　and　spin-ordered　(SO)　phases　co-exist　to　construct　an　asymmetric　spin　configuration　of　neighboring　active　sites.　The　replacement　of　axially　coordinated　H2O　molecules　with　TEMPOL　radicals　introduces　spin-spin　interactions　among　the　Cu(II)　centers　to　form　localized　SO　phases　within　the　original　H2O-mediated　SDO　phases.　Therefore,　TEMPOL@HKUST-1　derived　catalyst　exhibited　an　approximately　two-fold　enhancement　in　ethylene　selectivity　during　the　CO2RR　at　−1.8　V　versus　Ag/AgCl　compared　to　pristine　HKUST-1.　In　situ　ATR-SEIRAS　spectra　indicate　that　the　spin　configuration　at　asymmetric　SO/SDO　sites　significantly　reduces　the　kinetic　barrier　for　*CO　intermediate　dimerization　toward　the　ethylene　product.　The　performance　of　the　spin　catalyst　is　further　improved　by　spin　alignment　under　a　magnetic　field,　resulting　in　a　maximum　ethylene　selectivity　of　more　than　50　%.　The　exploration　of　the　spin-polarized　kinetics　of　the　CO2RR　provides　a　promising　path　for　the　development　of　novel　spin　electrocatalysts　with　superior　performance.　©　2024　Wiley-VCH　GmbH.