Nanomaterials have been shown to exhibit many unique optical properties that could directly affect advancements including solar cells1, medical imaging2, and light emitting diodes3. A subclass of nanoparticles called magic-sized clusters (MSCs) have shown even more novel properties due to their ultrasmall size (<2 nm) and atomically precise core and shell. Recent work has focused mainly on synthesis methods and defining the overall structure to better understand the fundamentals of nanoparticles in general. The next logical step would be to assemble these MSCs into functional materials which could provide a range of applications due to their unique properties. This study investigates strongly polarized CdS MSCs in liquid solution, isotropic films, and aligned thin films. The MSCs are able to form large, ordered domains from the hexagonal mesophase that generates single micrometer band structures. These films are assembled through three simple methods including shearing, cantilever, and unidirectional drying. In addition, the polarized optical properties of the MSCs in liquid and films were investigated through fluorescence anisotropy. This is an important tool to define the polarized emission and orientation of the absorption and emission dipole moments of the clusters. We proved the highly polarized properties of the MSCs with significantly high anisotropy values especially with the aligned films. Assembly of nanomaterials at an air-water interface has also been proven to provide an easy and simple method to form functional films. The CdS MSCs were studied at this interface and exhibited promising results for future studies. The difficulty lies with the small size of the clusters and the ligands, effecting the overall assembly of the monolayer as well as the characterization of the assembled films.