We report on the formation of nanocolumnar junctions of metal oxide and metal nanowires, i.e., (Cu22222O/Ni structures into an alumina template were prepared by two electrochemical steps in sequence, galvanostatic-potentiostatic deposition and vice versa. The deposition rate of Ni was seven times faster than the CuO)-O-O/Ni and ZnO/Ni by a single electrodeposition technique in this work. In addition, metal oxide junctions on Ni nanowires, i.e., Cu-O-O/ZnO/Ni and ZnO/Cu-O-O formation rate, but Cu consumed slightly more charge to form nanowires with the same aspect ratio. ZnO was formed by electrochemical reduction followed by physical dehydration and its deposition rate was 0.17 mm/min. Scanning electron microscopy morphological observation and energy dispersive X-ray analysis clearly showed distinct structures of nano-columnar metal/metal oxide inside the porous alumina template. 2005 The Electrochemical Society. All rights reserved.