This contribution summarizes efforts in designing, assembling/synthesizing, and structurally and functionally characterizing nanostructured materials using anodized aluminum oxide (AAO) as a thin-film template. Optical waveguide spectroscopy, using a nanoporous template as the guiding structure, is a particularly powerful analytical tool. The layer-by-layer approach for the fabrication of multilayer assemblies is shown to allow the fabrication of nanotube arrays. In addition to using dendrimers as building blocks, semiconducting nanomaterial (e.g., quantum dot) hybrid architectures with very interesting photophysical properties can be assembled. These can be employed, for example, in biosensing applications. Other strategies for using the AAO layers as templates include the growth of polymeric nanorod arrays from different functional monomers, which, after the dissolution of the template, are still able to guide light. This opens up novel concepts for integrated optics platforms with nanostructured materials.