In a step-wise combination of bottom-up and top-down approaches (illustrated in Fig. ), we first self-assemble ligand-functionalized NCs into ordered superstructures. Their microstructure is controlled with an emulsion-based self-assembly technique that allows us to tune the size and morphology at the micro-scale while still maintaining a large yield of the obtained spherical supraparticles (SPs). The resulting clusters are then used as secondary (higher hierarchical level) building blocks by embedding them in a polymeric matrix via vacuum infiltration with an epoxy resin. Inspired by the composite's design of natural materials such as nacre, we aimed for an increased toughness of the material system. Hence, an epoxy composition containing long oligomeric precursors with a high epoxy and amine hydrogen equivalent weight was chosen, leading to a low mesh density and therefore to a rubber-like behavior of the cured thermoset (more information available in the SI, Ch. 2).