A catalytic reaction over a silver catalyst performed in an unregarded temperature region(473—873 K) with a long catalytic lifetime for the production of methyl formate from methanol was provided as a potential preparing route. The optimal yield of methyl formate(ca. 14.8%) with a selectivity >90% was obtained at about 573 K. Because α-oxygen species and bulk oxygen species coexist in the unregarded temperature region, a synergistic process concerning α-oxygen species and bulk oxygen species was proved over O_α -rich and O_γ-rich samples. A catalytic reaction over a silver catalyst performed in an unregarded temperature region (473-873 K) with a long catalytic lifetime for the production of methyl formate from methanol was provided as a potential preparing route. The optimal yield of methyl formate (ca. 14.8 %) with a selectivity> 90% was obtained at about 573 K. Because α-oxygen species and bulk oxygen species coexist in the unregarded temperature region, a synergistic process concerning α-oxygen species and bulk oxygen species was proved over O-α -rich and O_γ-rich samples.