AbstractElectrochemical reduction of CO2 to value‐added chemicals is a promising strategy for the utilization of excess CO2. But, such reaction suffers from poor efficiency due to insufficient selectivity of electrocatalysts. Aimed at developing highly efficient electrocatalysts, dendritic Ag/Pd alloys with different compositions were synthesized through a simple galvanic replacement reaction. We found that the Ag/Pd alloy with an atomic ratio of 70 % Ag and 30 % Pd can selectively convert CO2 to CO with a maximum faradaic efficiency of 98.6 % and a current density of 9.3 mA/cm2 at −0.8 V, showing the best catalytic properties. Such improved performance can be ascribed to the factors that the introduction of Pd boosts the key intermediate formation and the dendrite morphology with a hydrophobic surface provides multiple active sites and increases CO2 concentration. This study may benefit the design of bimetallic alloy catalysts with improved activity and selectivity for CO2 reduction.