The reported copper nanoclusters (Cu NCs) of either CuII or CuI or mixed valence (MV) CuII/CuI or CuI/Cu0 characters are found to be stabilized with a discrete set of ligand donors; hence, analogous Cu NCs with a common architecture supported by the same or nearly the same donor set that exhibit different MV states of Cu, such as CuII/CuI and CuI/Cu0, are unknown. Such a series of highest nuclearity copper clusters supported by aromatic thiol-S donor ligands, namely [(L4)12CuI15CuII(μ4-S)](PF6)3 (1), [(MeL4)12CuI15Cu0(μ4-S)]ClO4·8C7H8 (2) and [(L4)12CuI15Cu02(DMF)](PF6)3·C2H5OH·2C7H8 (3), where XL4 = 2-((3-X-thiophen)-(2-yl-methylene)amino)-4-(trifluoromethyl)benzenethiol (X = H/Me), have been synthesized and their electronic structural properties have been examined and reported herein. The Cu16 NCs, 1 and 2, feature a central sulfido-S (Ss) bridged tetracopper SsCu4 core inside a sphere-shaped Cu12S12 truncated octahedron. As 1 and 2 have a non-metal (chalcogen or halogen) central atom (here Ss) instead of a metallic Cu core inside the Cu12S12 shell, they are of the inverse coordination complex (ICC) category, rather than superatomic with a core-shell (the core is a metal and the shell is a metal-ligand framework) structure. The NC 1, in the presence of polar solvents, converts to a two electron superatomic Cu17 NC, 3. The NC 3 features a trigonal pyramidal-shaped Cu4 core inside a modified Cu12S12, i.e. Cu13S12 shell. The transformation of 1 to 3 may be visualized as the replacement of the central sulfido-S by an extra Cu atom (generated from decomposed molecules of 1) and the shifting of a Cu atom of the SsCu4 unit to the Cu12S12 shell, resulting in a Cu13S12 shell. The present work offers the first example of (i) an ICC that has Cu0 character (i.e.2), (ii) a superatomic Cu NC (i.e.3) stabilized by an aromatic thiol-S donor ligand and (iii) spontaneous ICC (i.e.1) → superatomic NC (i.e.3) conversion that does not require any reducing agent, but rather occurs in the presence of a dioxygen oxidant. The probable mechanisms for the reversible 1 ↔ 3 conversions have been discussed. The presence of Ss in 1 and 2 unveils the first evidence of benzene thiol C-S bond cleavage, to the best of our knowledge. The spectroelectrochemical studies shed light on the choice of CuII/CuI and CuI/Cu0 character of 1 and 2, respectively, which is supported by high resolution XPS and Cu LMM Auger spectroscopy.