We report a new strategy to prepare a composite catalyst for highly efficient electrochemical CO2 reduction reaction (CO2RR). The composite catalyst is made by anchoring Au nanoparticles on Cu nanowires via 4,4′‐bipyridine (bipy). The Au‐bipy‐Cu composite catalyzes the CO2RR in 0.1 m KHCO3 with a total Faradaic efficiency (FE) reaching 90.6 % at −0.9 V to provide C‐products, among which CH3CHO (25 % FE) dominates the liquid product (HCOO−, CH3CHO, and CH3COO−) distribution (75 %). The enhanced CO2RR catalysis demonstrated by Au‐bipy‐Cu originates from its synergistic Au (CO2 to CO) and Cu (CO to C‐products) catalysis which is further promoted by bipy. The Au‐bipy‐Cu composite represents a new catalyst system for effective CO2RR conversion to C‐products. Joint action: Au nanoparticles were attached to Cu nanowires through a 4,4′‐bipyridine (bipy) linker to form the new composite catalyst Au‐bipy‐Cu. Thanks to the synergistic catalysis of Au (for CO2 to CO), Cu (for CO coupling), and bipy (for the CO2* stabilization and protonation), this catalyst demonstrates enhanced electrochemical reduction of CO2 to hydrocarbons.