AbstractFurfural hydrogenation over silica‐supported Co@Pd and Cu@Pd bimetallic overlayer catalysts was studied in this work. Both overlayer catalysts showed enhanced reactivity compared to pure Pd in furfural hydrogenation. Langmuir‐Hinshelwood kinetic study revealed that this enhanced reactivity could be attributed to the decreased hydrogen surface coverage on catalyst surface of overlayer catalysts compared to pure Pd during reaction, releasing more available active sites for surface reaction or furfural adsorption to take place. The effect of oxygen vacancy concentration on furfural hydrogenation product selectivity was also studied. It is proposed that oxygen vacancies were crucial for both furfural hydrodeoxygenation and aromatic ring hydrogenation, depending on the concentration of oxygen vacancies. This work provides new perspective for tuning the furfural hydrogenation product selectivity by altering the oxygen vacancy concentration.