CuO–Al 2 O 3 systems with different Cu/Al ratios were prepared by the amorphous citrate process, and their catalytic activities for the dehydrocoupling of methanol to methyl formate were examined. In the CuO–Al 2 O 3 systems, CuAl 2 O 4 samples calcined at temperatures below 1000°C were partially reduced during the reaction at 310°C and decreased the selectivity to methyl formate (MF) with increasing Cu(0) content. Cu(0) species catalyzed the dehydrocoupling reaction without decomposition of methyl formate at temperatures below 210°C, whereas Cu(0) decomposed methyl formate into methanol and CO above 210°C. On the other hand, CuAl 2 O 4 calcined at 1100°C showed the highest activity of the formation of methyl formate at a reaction temperature of 310°C. Since the CuAl 2 O 4 sample was not reduced even at 310°C, Cu(II) species in the CuAl 2 O 4 were found to be effective sites for the dehydrocoupling at temperatures above 250°C. In addition, Cu(I) species in CuAlO 2 was also found to be active with keeping high MF selectivity up to 290°C.