Vacuum anneal induced changes in the surface layers of electrodeposited copper(I) oxide (Cu2O) were probed by time-of-flight positron annihilation induced Auger electron spectroscopy (TOF-PAES) and by electron induced Auger electron spectroscopy (EAES). Large changes in the intensity of the Cu PAES intensity resulting from isochronal in situ vacuum anneals made at increasing temperatures indicated that, before thermal treatment, the surface was completely covered by a carbonaceous overlayer and that this layer was removed, starting at a temperature between 100 and 200 degrees C, to expose an increasing amount of Cu in the top layer as the anneal temperature was increased. The thickness of this overlayer was estimated to be similar to 4 A based on analysis of the EAES data, and its variation with the thermal anneal temperature was mapped. This study demonstrated the order-of-magnitude enhancement in the sensitivity of PAES to the topmost surface layer in Cu2O relative to the EAES counterpart; factors underlying this contrast are discussed. Finally, the implications of ultrathin carbon layers on semiconductor surfaces are discussed.