Abstract: Au-Pd/SiO₂ catalysts with different calcination temperatures were prepared by sol-immobilization method; their catalytic performance in oxidation of methanol to methyl formate was investigated. Among 200~500℃, Au-Pd/SiO₂ catalyst calcined at 400℃ exhibits the best catalytic activity in the topic reaction at room temperature, and 25.3% methanol conversion with 100% selectivity to methyl formate can be achieved at100℃. They were characterized by BET, XRD, UV-vis DRS, XPS, TEM and DRIFTS. Good dispersity of Au and Pd, proper particle size of Au and Pd, the formation of Au-Pd bimetallic nanoparticles, and strong interaction between Au and Pd in the Au-Pd/SiO₂ catalyst are beneficial to the oxidation of methanol to methyl formate. Furthermore, a preliminary reaction mechanism of methanol oxidation to methyl formate on the Au-Pd/SiO₂ catalyst is inferred and methyl formate is gained from intermediate species methoxy in this reaction mechanism.