Electrocatalytic　CO　reduction　(COR)　offers　a　promising　alternative　approach　for　synthesizing　valuable　chemicals,　potentially　at　a　lower　carbon　intensity　as　compared　to　conventional　chemical　production.　Cu-based　catalysts　have　shown　encouraging　selectivity　and　activity　toward　multi-carbon　(C2+)　products,　albeit　typically　in　the　form　of　a　mixture.　Steering　COR　selectivity　toward　specific　types　of　C2+　products,　such　as　liquid　products　with　high　energy　density,　remains　a　challenge.　In　this　study,　we　developed　a　Cu/Zn　bimetallic　catalyst　composite　and　demonstrated　enhanced　selectivity　toward　liquid　products　as　compared　to　reference　CuO　and　Cu-based　catalysts,　approaching　60%　at　a　high　current　density　of　300　mA/cm2.　Our　investigation　highlights　that　the　introduction　of　Zn　promoted　the　emergence　of　a　Cu/Zn　heterojunction　interface　during　COR.　Density　functional　theory　simulations　were　used　to　rationalize　the　observed　differences　in　selectivity,　revealing　that　interface　plays　a　crucial　role　in　diminishing　the　oxygen　adsorption　at　the　Cu-sites　and　modifying　the　adsorption　energy　of　COR　reaction　intermediates,　consequently　leading　to　enhanced　selectivity　toward　liquid　products.　©　2025　The　Author(s).　SmartMat　published　by　Tianjin　University　and　John　Wiley　&　Sons　Australia,　Ltd.