Porous anodic aluminum oxide (AAO) films can be conveniently produced by anodization of aluminum. Porous oxide layer formed on aluminum contains a large number of mutually parallel pores. Each cylindrical nanopore and its surrounding oxide constitute a hexagonal cell aligned normal to the metal surface. Under proper conditions, the oxide cells are self-organized to form a hexagonally close-packed structure. The novel and tunable structural features of porous AAOs have been intensively exploited for templated synthesis of a variety of functional nanostructures and also for fabrication of nanodevices. On the other hand, porous AAOs with modulated pores may provide an additional degree of freedom in templated synthesis. In addition, they can be used as model systems for systematically investigating structure-property relations of nanostructured materials. Based on the anodization techniques developed recently, one can fabricate porous AAOs with tailor-made internal pore structures. This chapter is devoted to conveying the most recent advances in structural engineering of porous AAOs and nanotechnology applications. In order to provide context, a brief description is given of the general structure and fundamental electrochemical processes associated with pore formation. Subsequently, two common anodizing techniques (i.e., mild and hard anodizations) that have been explored for nanotechnology applications are discussed. Next, various nanostructuring approaches for custom-designed porous AAOs are reviewed. The chapter covers the properties of porous AAOs derived from structural engineering and their applications to various nanotechnology researches and finally presents the challenges and future prospects.