Successive oxidation of an amorphous Cu41Zr59 alloy followed by reaction generates an active and selective catalyst in the dehydrogenation of methanol to methyl formate (about 80% selectivity at 40% conversion at 220 degrees C). The high activity and selectivity of the catalyst thus formed can be maintained for a long period (over 150 h on stream). A similar activation of Cu-Ti and Cu-Hf was unsuccessful. The comparison of Cu(0) surface areas determined in situ or after reducing the used catalysts in hydrogen indicates that oxidized copper species are the active sites in the transformation.