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 Oα -rich and Oγ-rich samples.