Ligand-protected metal clusters, which consist of a finite number of noble metal atoms (such as gold and silver), exhibit size-or composition-dependent luminescence properties, magnetic behavior, and catalytic activity. Owing to these characteristics, they are expected to be applied in luminescent materials, magnetic memory devices, and oxidation catalysts. The shape of the electronic orbitals in metal clusters resembles that of atomic orbitals (s, p, d, etc). Therefore, metal clusters can be regarded as "superatoms". In recent years, three main approaches (Scheme S1) have been explored for developing materials using superatoms as fundamental building units i.e.,: (1) fusing superatomic cores to form superatomic molecules; (2) arranging and crystallizing metal clusters into superlattice structures, driven by interactions between surface ligands of adjacent clusters; and (3) linking metal clusters through ligand exchange reactions with bridging ligands to form covalently bonded assemblies. The materials obtained through these approaches exhibit absorption and emission properties, as well as catalytic activity, that differ from those of individual metal clusters. Consequently, the fabrication of materials using metal clusters as building units has garnered attention as an effective strategy for unlocking novel properties based on metal clusters. However, core fusion between metal clusters in approach (1) is complex, thereby hindering its universal application to different systems. In approach (2), where crystal growth is driven by isotropic interactions between metal cluster surfaces, only a limited range of packing structures can be achieved. In approach (3), where metal clusters are linked via ligand exchange reactions, reaction control is challenging, often leading to the formation of randomly connected assemblies or amorphous polymers with multiple linkages. Therefore, designing and precisely synthesizing metal cluster assemblies with the desired structures using approaches (1)-( ) is a significant challenge.