The preparation of one-dimensional nanostructures and microstructures by means of inert, shape-defining molds, such as anodic aluminum oxide and macroporous silicon, is a well established and intensively investigated methodology. Up to know, however, little effort has been made to rationally explore the intrinsic reactivity of these commonly used template materials. This is astounding since reactive templates may pave the way for new synthetic routes to tubes and wires not accessible otherwise that consist of complex functional materials or exhibit core/shell morphology. Here we summarize recent advances regarding this emerging approach with special emphasis on self-ordered anodic aluminum oxide whose pore walls consists of an amorphous, highly reactive alumina scaffold.