Porous, high surface area materials have critical roles in applications including catalysis, photochemistry, and energy storage. In these fields, researchers have demonstrated that the nanometer-scale structure modifies mechanical, optical, and electrical properties of the material, greatly influencing its behavior and performance.Such complex chemical systems can involve several distinct processes occurring in series or parallel. Understanding the influence of size and structure on the properties of these materials requires techniques for producing clean, simple model systems. In the fields of photoelectrochemistry and lithium storage, for example, researchers need to evaluate the effects of changing the electrode structure of a single material or producing electrodes of many different candidate materials while maintaining a distinctly favorable morphology.In this Account, we introduce our studies of the formation and charac-terization of high surface area, porous thin films synthesized by a process called reactive ballistic deposition (RBD). RBD is a simple method that provides control of the morphology, porosity, and surface area of thin films by manipulating the angle at which a metal-vapor flux impinges on the substrate during deposition. This approach is largely independent of the identity of the deposited material and relies upon limited surface diffusion during synthesis, which enables the formation of kinetically trapped structures.Here, we review our results for the deposition of films from a number of semiconductive materials that are important for applications such as photoelectrochemical water oxidation and lithium ion storage. The use of RBD has enabled us to systematically control individual aspects of both the structure and composition of thin film electrodes in order to probe the effects of each on the performance of the material. We have evaluated the performance of several materials for potential use in these applications and have identified processes that limit their performance. Use of model systems, such as these, for fundamental studies or materials screening processes likely will prove useful in developing new high-performance electrodes.