Polymetallic　electrocatalysts　represent　as　a　promising　strategy　for　steering　the　electrocatalytic　CO2　reduction　reactions　(eCO2RR)　toward　valuable　products.　However,　achieving　simultaneous　high　selectivity　and　activity　remains　challenging.　Here,　we　report　a　dual-doped　CuO　catalyst　(CuO-Sn0.02-Ga0.005)　that　synergistically　combines　Sn　and　Ga　to　achieve　exceptional　performance　for　CO2-to-CO　conversion.　Electrochemical　evaluations　demonstrate　that　the　optimized　catalyst　exhibits　a　Faradaic　efficiency　(FE)　of　99.37　%　for　CO　at　-0.7　VRHE　with　a　current　density　of　-132.8　mA　cm-2,　significantly　outperforming　pristine　CuO　(54.21　%,　-47.6　mA　cm-2　and　single-doped　counterparts　(93.50　%,　-55.3　mA　cm-2　for　CuO-Sn0.02　and　46.76　%,　-94.2　mA　cm-2　for　CuO-Ga0.02,　respectively).　Sn　doping　suppresses　hydrogen　evolution　and　enhances　CO　selectivity,　while　Ga　doping　boosts　catalytic　activity.　In　situ　Raman　spectroscopy　reveals　that　Sn　incorporation　facilitates　the　stabilization　of　key　intermediates　(e.g.,　*COOH),　whereas　Ga　introduces　lattice　strain　and　defects,　enlarging　the　electrochemically　active　surface　area.　The　catalyst　also　demonstrates　remarkable　stability,　maintaining　＞95　%　FE　for　CO　over　75　h.　This　work　provides　a　rational　design　strategy　for　non-precious　metal　catalysts　through　dual-element　doping,　highlighting　the　critical　role　of　electronic　and　structural　modulation　in　eCO2RR.　©　2025　Elsevier　Ltd