In　the　electrochemical　CO2　reduction　reaction　(CO2RR),　the　coverages　of　*CO　and　*H　intermediates　on　a　catalyst　surface　are　critical　for　the　selective　generation　of　C1　or　C2　products.　In　this　work,　we　have synthesized　several　CuxZnyMnz　ternary　alloy　electrocatalysts,　including　Cu8ZnMn,　Cu8Zn6Mn,　and　Cu8ZnMn2,　by　varying　the　doping　compositions　of　Zn　and　Mn,　which　are　efficient　in　binding　*CO　and　*H　adsorbates　in　the　CO2　electroreduction　process,　respectively.　The　increase　of　*H　coverage　allows　to　promotion　of　the　CH4　and　H2　formation,　while　the　increase　of　the　*CO　coverage　facilitates　the　production　of　C2H4　and　CO.　As　a　result,　the　Cu8ZnMn　catalyst　presented　a　high　CO2-to-CH4　partial　current　density　(−418 ± 22 mA cm−2)　with　a　Faradaic　efficiency　of　55 ± 2.8%,　while　the　Cu8Zn6Mn　catalyst　exhibited　a　CO2-to-C2H4　partial　current　density　(−440 ± 41 mA cm−2)　with　a　Faradaic　efficiency　of　58 ± 4.5%.　The　study　suggests　a　useful　strategy　for　rational　design　and　fabrication　of　Cu　electrocatalysts　with　different　doping　for　tailoring　the　reduction　products.　©　2023　Wiley-VCH　GmbH.