The　electrochemical　reduction　of　CO2　to　produce　high-value　multicarbon　products　represents　a　challenging　yet　highly　desirable　process,　particularly　due　to　the　inefficient　C-C　coupling　observed　in　current　electrocatalysts.　In　this　study,　Cu2+　and　Co2+　were　introduced　into　ZIF-8　as　precursors　to　synthesize　a　series　of　Co-　and　CuCo-doped　carbon　nanostructure　materials　with　varying　Co-to-Cu　ratios.　X-ray　diffraction　and　X-ray　photoelectron　spectroscopy　(XPS)　analyses　confirmed　the　successful　doping　of　metal　Co　in　the　form　of　Co-Nx,　while　Cu　was　partly　doped　as　nanoparticles　attached　to　the　carbon　substrate　surface　and　partly　as　single　atoms　forming　Cu-Nx.　Transmission　electron　microscopy　and　energy-dispersive　X-ray　spectroscopy　analyses　revealed　uniform　distribution　of　elemental　Co　and　Cu　on　the　carbon　substrate,　with　Cu　loaded　as　nanocluster　on　the　surface.　Linear　sweep　voltammetry　tests　indicated　that　Cu/CoCu-Nx-C　composites　exhibited　enhanced　reactivity　toward　CO2　reduction　compared　to　other　samples.　At　−0.19　V　(vs　RHE),　the　Faradaic　efficiencies　(FEs　%)　of　C2H4,　C2H6,　CH4,　CO,　and　H2　over　Cu/CoCu-Nx-C　were　29.7,　8.6,　20.2,　9.8,　and　31.5%,　respectively.　The　influence　of　Co　and　Cu　doping　modes　on　the　selectivity　of　electrocatalytic　reduction　products　was　investigated.　Results　showed　that　Cu/CoCu-Nx-C　exhibited　a　higher　FE　of　C2　compared　to　Cu/Cu-Nx-C,　with　nearly　10　times　higher　C2　current　density.　Mechanistic　insights　from　acid-etching　experiments　and　XPS　revealed　a　synergistic　interaction　between　metallic　Co　and　Cu,　promoting　the　generation　of　multicarbon　products.　Co-Nx　improved　*CO　coverage,　facilitating　subsequent　C-C　coupling　on　neighboring　Cu-Nx.　Additionally,　CH4　production　was　attributed　to　the　(111)　crystalline　facets　in　the　Cu　nanocluster　and　isolated　Cu-Nx.　Overall,　this　research　provides　an　important　understanding　of　the　creation　of　straightforward　and　effective　catalysts　for　the　reduction　of　CO2.　It　holds　considerable　potential　for　the　production　of　hydrocarbons　using　carbon　dioxide.　©　2024　American　Chemical　Society.