Clusters of gold atoms can be viewed as superatoms, in which valence electrons confined in the particles occupy atomic-like, discrete electronic levels. Chemical modification of the gold superatoms and their aggregated molecules (superatomic molecules) with organic ligands is a promising approach for their application as the building units of new functional materials. This account surveys the present status of the rapidly growing field of gold superatoms and superatomic molecules protected by thiolates and phosphines. The major aim of this article is to provide a simple picture for the structure, stability and bonding scheme of chemically modified superatoms and superatomic molecules for the development of a new class of hierarchical materials.