Catalysts prepared from NaH, tert-amyl alcohol and nickel acetate are effective for low-temperature methanol synthesis in organic solvents. Results of reactions with a single component or several components of the catalyst suggested that nickel acetate activated by NaH was responsible for the methanol formation. The XAFS (X-ray absorption fine structure) study of the catalysts revealed that nickel acetate in the catalyst was transformed into nickel tetracarbonyl under the reaction conditions. A combined catalyst composed of nickel tetracarbonyl and alkali alkoxide was highly active for the selective formation of methanol from synthesis gas, suggesting that nickel tetracarbonyl formed in the reaction was involved in the methanol synthesis.