Cluster assembling has been one of the hottest topics in nanochemistry. In certain ligand-protected gold clusters, bi-icosahedral cores assembled from Au 13 superatoms were found to be analogues of diatomic molecules F 2 , N 2 , and singlet O 2 , respectively, in electronic shells, depending upon the super valence bond (SVB) model. However, challenges still remain for extending the scale in cluster assembling via the SVB model. In this work, ligand-protected tri-and tetra-superatomic clusters composed of icosahedral M@Au 12 (M = Au, Pt, Ir, and Os) units are theoretically predicted. These clusters are stable with reasonable highest occupied molecular orbital (HOMO)−lowest unoccupied molecular orbital (LUMO) energy gaps and proven to be analogues of simple triatomic (Cl 3 − , OCl 2 , O 3 , and CO 2 ) and tetra-atomic (NC−CN, and Cl−CC−Cl) molecules in both geometric and electronic structures. Moreover, a stable clusterassembling gold nanowire is predicted following the same rules. This work provides effective electronic rules for cluster assembling on a larger scale and gives references for their experimental synthesis.