Producing　Cn　products　through　electrocatalytic　CO2　reduction　reaction　(CO2RR)　is　of　great　significance　in　addressing　the　global　warming　crisis.　Organic-inorganic　hybrid　catalysts,　characterized　by　precise　and　controllable　active　sites　and　metal-ligand　synergistic　interactions,　can　enhance　the　reaction　activity　and　stability　of　Cu-based　catalysts.　Herein,　based　on　density　functional　theory　(DFT),　a　novel　flexible　aromatic　Cu3　metal-organic　π-cluster　(Cu3-π　cluster)　was　constructed,　consisting　of　triple-atom　active　centers　and　pentalyne　ligands.　During　the　catalytic　CO2RR　process,　the　adsorption　of　H　can　promote　the　activation　of　CO2,　this　converts　the　competing　hydrogen　evolution　reaction　(HER)　into　promoting　CO2RR.　Enhanced　aromaticity　of　its　cluster　core　is　credited　with　stabilizing　the　coadsorption　of　H　and　CO2　(H*　+　CO2*),　consequently　lowering　the　reaction　free　energy　of　the　CO2　activation　process.　Research　has　shown　that　Cu3-π　cluster　have　high　catalytic　activity　for　electrocatalytic　CO2　generation　of　C2H4.　Considering　the　solvation　effect,　the　limit　potential　of　this　reaction　is　−0.60　V.　Furthermore,　the　reaction　free　energies　suggest　that　the　Cu3-π　cluster　is　more　inclined　to　yield　C2H4(g)　products　via　COCO*　coupling.　Moreover,　the　high　CO　coverage　at　the　triple-atom　active　centers　not　only　makes　it　more　challenging　for　this　cluster　to　adsorb　H,　but　also　reduces　the　energy　barrier　of　the　COCO*　coupling　reaction.In　the　entire　reaction　pathway　of　C2H4(g),　there　exhibits　dynamic　self-adaptive　behavior　in　the　bond　lengths　and　bond　angles　of　the　three　Cu　atoms　in　the　cluster　core,　leading　to　fluctuations　in　aromaticity.　The　flexibility　and　aromaticity　changes　in　this　structure　enable　the　Cu3-π　cluster　to　better　stabilize　intermediates.　This　work　provides　theoretical　guidance　for　the　application　of　metal-organic　π-clusters,　accelerates　the　screening　of　catalysts　for　CO2RR,　and　provides　powerful　theoretical　guidance　for　the　structure-activity　relationships　between　aromaticity　and　catalytic　activity.　©　2024