AbstractHerein, we report a series of CuPd catalysts for electrochemical hydrogenation (ECH) of furfural to 2‐methylfuran (MF or FurCH3 where Fur=furyl) in aqueous 0.1 M acetic acid (pH 2.9). The highest faradaic efficiency (FE) for MF reached 75 % at −0.58 V vs. reversible hydrogen electrode with an average partial current density of 4.5 mA cm−2. In situ surface‐enhanced Raman spectroscopic and kinetic isotopic experiments suggested that electrogenerated adsorbed hydrogen (Hads) was involved in the reaction and incorporation of Pd enhanced the surface coverage of Hads and optimized the adsorption pattern of furfural, leading to a higher FE for MF. Density functional theory calculations revealed that Pd incorporation reduced the energy barrier for the hydrogenation of FurCH2* to FurCH3*. Our study demonstrates that catalyst surface structure/composition plays a crucial role in determining the selectivity in ECH and provides a new strategy for designing advanced catalysts for ECH of bio‐derived oxygenates.