X-ray photoelectron spectroscopy was used for surface characterization of amorphous Cu-M alloy powders (Cu40Ti60, Cu50Zr50, and Cu65Hf35) produced by mechanical alloying of the constituents, When used as catalyst in the dehydrogenation of alcohols Cu-Zr and Cu-Hf were found to undergo structural changes resulting in surface copper enrichment with a substantial fraction of copper being in fully reduced, metallic (Cu-0) state. This result accounts for the high and stable catalytic activity of Cu-Zr and Cu-Hf in the transformations of alcohols. In contrast, when Cu-Ti is used in inert atmosphere, surface enrichment of titanium is observed. Although segregation of copper occurs in the presence of hydrogen, only oxidized copper species are detected on the surface. In either case, the catalytic activity of Cu-Ti is inferior to the other two alloy samples. TiH2 is shown by XRD to be the characteristic species formed under hydrogen. This is stable in the presence of hydrogen and, therefore, Cu acts as an oxygen scavenger and forms oxidized surface species that do not show catalytic activity.