As reported previously, the size of the SPs can be adjusted by tailoring the surfactant formulation so as to systematically obtain a controlled SP diameter, in this case of 1.3±0.7 µm (Fig. ). This SP size was selected so as to achieve the largest possible superstructures while still limiting the occurrence of imperfections within the SPs, like cracks (Fig. ), which would act as preexisting material's flaws limiting the final composite's robustness. SEM confirms that the assembled SPs consist of an ordered arrangement of NCs (Fig. ). Due to long-range Bragg reflections arising in the small-angle X-ray scattering (SAXS) signal for highly ordered particles, SAXS was used to further characterize the supercrystalline structure, as described previously. The relative peak positions corresponding to lattice planes are consistent with a face-centered-cubic (FCC) structure. While the majority of the SPs exhibit single FCC structures (as the example shown in Fig. ), polycrystalline and partially amorphous arrangements can also be observed. This is ascribed to differences in the drying profile of each emulsion droplet, depending on its local position and environment during the self-assembly process. Furthermore, the random orientation of the SPs in the polymer matrix causes the appearance of Debye-Sherrer rings in the SAXS signal (Fig. ) confirming an isotropic polycrystalline structure at the nanoscale. The distance between the superlattice planes in the as-obtained SPs indicates interparticle distances of 1.3 ± 0.1 nm, which is below the calculated length of the corresponding extended ligand molecule (∼ 2.0 nm). Therefore, the self-assembly results in superlattices in which the ligands interfacing the NCs are interdigitated and/or bent, as depicted in Fig. .