Some chromium-free copper-based catalysts are tested for the gas-phase hydrogenolysis of methyl formate, in which Cu-B2O3/SiO2 catalyst is identified to be the most promising. The behaviors of Cu-B2O3/SiO2 catalysts are also examined in the slurry-phase hydrogenolysis of methyl formate, along with a discussion of the promoting effect of B2O3. Also, Cu-B2O3/SiO2 is used with potassium methoxide as a co-catalyst for the carbonylation of methanol to regenerate the potassium methoxide from potassium formate and potassium methyl carbonate. Moreover, the slurry-phase one-step synthesis of methanol is studied using KOCH3/Cu-B2O3/SiO2 mixed catalyst under relatively mild conditions.