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Porous alumina membranes have attracted much attention because they are very useful templates for the fabrication of various nanostructures important to nanotechnology. However, there are challenges in controlling pore geometries and interpore distances in alumina templates while maintaining highly ordered hexagonal pore structures. Herein, a three-step anodization method is utilized to prepare anodic alumina templates with various pore morphologies (e.g., arched-shape, tree-like, branched-shape) and tunable interpore distances. Such structures are not found within the more traditional alumina templates fabricated by a two-step anodization of aluminum films. The range of interpore distances and pore diameters within the modified templates increases with increasing voltages. In contrast, under decreasing voltages, hexagonally ordered pores can also branch into several pores with smaller sizes and reduced interpore distances. Electrochemical growth of metal nanowires in the modified templates helps to highlight details of the pore structures and which pore channels are active.