Nanolayers of Cu and Cu2O with a wide range of layer thicknesses have been produced using pulsed galvanostatic and potentiostatic electrodeposition from alkaline Cu(II)-citrate solutions. The thicknesses of the individual Cu and Cu2O layers can be independently controlled and the composition of the multilayered materials, which also were studied using electrochemical quartz crystal microbalance, X-ray diffraction, and scanning electron microscopy, can be varied from pure Cu to pure Cu2O by varying the current density or the deposition potential. It is shown that some of the deposited Cu2O is reduced during the subsequent copper deposition step and that the influence of this effect depends on the Cu (II) concentration, the Cu2O microstructure, and the deposition mode. Additional Cu2O deposition is demonstrated to take place after the copper deposition step due to comproportionation and precipitation of Cu2O. This effect facilitates electrodeposition of Cu2O on Cu. Deposition of Cu on the Cu2O layer formed by comproportionation and precipitation was likewise found to be more straightforward than on electrodeposited Cu2O. Well-defined nanolayered Cu/Cu2O materials are generally best manufactured using pulsed galvanostatic techniques because a much larger fraction of the Cu2O was found to be reduced during the subsequent Cu deposition pulse in pulsed potentiostatic depositions. (c) 2007 The Electrochemical Society.