Cu-based catalysts such as Cu/Cr/Mn are active catalysts in the decomposition of methanol to CO and H-2. It was found that the activity of the Cu/Cr/Mn catalyst can be enhanced by adding small amounts of alkali additives in the catalyst. The promoting effect increased in the order of Li, Na and K. The formation of dimethylether as a result of dehydration of methanol decreased with the addition of alkali additives. Catalyst characterizations indicate that alkali promoters reduce the BET surface area of the catalysts but significantly enhance the dispersion of active copper. The latter contributes to the increased activity.