Less methanol is being adsorbed at 25 degrees C, and decomposed during temperature-pro rammed desorption (TPD) on copper-containing catalysts CuO/ZrO2 and CuO/ZnO/ZrO2 than on the copperless catalysts ZrO2 and ZnO/ZrO2. On this last class of solids the concentration of hydroxyl groups decreases by adsorption of methanol whereas the reverse is observed on copper-containing catalysts, where also lower temperatures are required for the transformation of the methoxy groups into more oxidized species such as formate and carbonates. The influence of copper on these processes is explained by the spillover of hydrogen, through copper ions, from the methoxy groups to oxygen ions of zirconia.