A new procedure for preparing free-standing nanowire arrays is described. This is based on a template method which entails electrochemical metal deposition into nanometer-wide parallel pores of porous anodic oxide films on aluminum. By varying the preparation conditions and by applying electrochemical posttreatment methods, gold nanowire arrays are prepared, whose morphological and dimensional properties and oxygen content in the nanowire surface can be varied and investigated by SEM and XPS-characterization. The voltammetric behaviour of such nanowire arrays shows a significant enhancement of the ratio between the total electrolytically exposed surface area and the diffusionally accessible surface area in comparison with macroscopic flat gold electrodes.