The　construction　of　biomimetic　cluster　catalysts　with　metalloenzyme-like　active　sites　may　open　an　avenue　for　the　challenging　transformation　of　greenhouse　gases　(e.g.,　CO2)　to　high-value　chemicals.　Cu-enzymes　occur　in　all　three　biological　kingdoms,　with　CuZ　clusters　serving　as　representative　reaction　sites　that　catalyze　challenging　transformations.　However,　artificial　Cu　clusters　with　analogous　CuZ　structures　and　high　stability　are　still　rare.　In　this　work,　we　have　successfully　adopted　a　Ti9-oxo　nanoring　as　an　inorganic　templating　scaffold　to　isolate　a　small　Cu4　cluster,　which　can　be　regarded　as　a　atomically　precise　bioinspired　cluster　with　metalloenzyme-like　catalytic　sites　(CuZ).　Importantly,　Cu4@Ti9　displays　high　selectivity　for　the　electrocatalytic　reduction　of　CO2　to　C2H4　(FE:　47.6　±　3.4%)　at　400　mA　cm-2　and　good　catalytic　durability　(8　h).　The　bioinspired　Cu4@Ti9　not　only　represents　the　first　example　of　Cu　cluster　directly　encapsulated　by　a　metal-oxo　shell　but　also　opens　the　CO2　electroreduction　to　ethylene　applications　of　atomically　precise　metallic　clusters.　©　2023　American　Chemical　Society.