Thiolates are a widely used ligand class for the stabilization of M(0)-containing gold and silver nanoclusters. Curiously, though, very few thiolate-stabilized Cu nanoclusters are known. Herein, we report an examination of the reactivity of RSH (R = CH2CH2Ph, n-Bu, n-C12H25) with Cu2+ under anhydrous conditions. These reactions result in the formation of fluorescent "Atlas-sphere"-type copper thiolate nanoclusters, including [Cu-12(SR')(6)Cl-12][(Cu(R'SH))(6)] (2, R' = '' Bu) and [H(THF)(2)](2) [Cu-17(SR '')(6)Cl-13 (THF)(2) (R '' SH)(3)] (3, R '' = CH2CH2Ph), which were characterized by X-ray crystallography, electrospray ionization mass spectrometry, NMR spectroscopy, as well as X-ray absorption near-edge structure and extended X- ray absorption fine structure (EXAFS) spectroscopies. Consistent with our X-ray crystallographic results, the edge energies of 2 and 3 suggest they are constructed exclusively with Cu(I) ions. Similarly, EXAFS of 2 and 3 reveals long Cu-Cu pathlengths, which is also consistent with their X-ray crystal structures. Given these results, as well as past work on Cu2+/thiol reactivity, we suggest that Cu(0) is unlikely to be formed by the reaction of Cu2+ with a thiol and that previous reports of Cu(0)-containing nanoclusters synthesized by reaction of Cu2+ with thiols are likely erroneous.