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Nanostructured materials promise to unlock new functionality that can address modern challenges in electronics, health, and infrastructure. However, to fully hardness the power of size-based effects, we need to develop new methods for designing microstructurally complex and heterogeneous nanostructures. Furthermore, deep fundamental understanding of designed nanoscale materials is critical for bringing these tools to the materials engineers of tomorrow. Using nanoscale additive manufacturing, we will explore new pathways for nanoscale materials design and investigate the emerging materials behaviors that arise at the intersection of geometric and microstructural size-effects. Insights from studies on nanocrystalline nano-architected ZnO and nanoporous Ag will begin to untangle the intricate roles of processing and microstructure in advancing nanoscale materials performance.