Electrochemical CO reduction reaction (CO RR) is a promising strategy for waste CO utilization and intermittent electricity storage. Herein, it is reported that bimetallic Cu/Pd catalysts with enhanced *CO affinity show a promoted CO RR performance for multi-carbon (C2+) production under industry-relevant high current density. Especially, bimetallic Cu/Pd-1% catalyst shows an outstanding CO -to-C2+ conversion with 66.2% in Faradaic efficiency (FE) and 463.2 mA cm in partial current density. An increment in the FE ratios of C2+ products to CO  for Cu/Pd-1% catalyst further illuminates a preferable C2+ production. In situ Raman spectra reveal that the atop-bounded CO is dominated by low-frequency band CO on Cu/Pd-1% that leads to C2+ products on bimetallic catalysts, in contrast to the majority of high-frequency band CO on Cu that favors the formation of CO. Density function theory calculation confirms that bimetallic Cu/Pd catalyst enhances the *CO adsorption and reduces the Gibbs free energy of the CC coupling process, thereby favoring the formation of C2+ products.