The reaction of AuCl(SMe2) with equimolar NaO5NCS2 [O5NCS2 = (aza-18-crown-6)dithiocarbamate] in CH3CN gave [Au-2(O5NCS2)(2)]center dot 2CH(3)CN (2 center dot 2CH(3)CN), where six other 2 center dot solvates (solvates = 2DMF, 2DMSO, 2THF, 2acetone, 1.5toluene, and 1.5anisole) can be successfully isolated from different crystal-growing processes (i.e., ether diffusion, layer method, or evaporation in air) by dissolving the dry powder samples of 2.2CH(3)CN in the respective solvents, and their crystal structures are all determined by X-ray diffraction as well. It is noted that there are different intermolecular Au(I)center dot center dot center dot Au(I) contacts in combination with various luminescences for 2 center dot solvates and indeed there is a close relationship between intermolecular Au(I)center dot center dot center dot Au(I) contacts [i.e., 2.8254(7)-2.9420(5) angstrom] and luminescence energies (i.e., 554-604 nm), including three examples of 2 center dot 2CH(3)CN, 2. 0.5m-xylene, and 2 center dot tert-butylbenzene center dot H2O reported in our previous work. In 2 center dot solvates, the toluene and tert-butylbenzene solvates have the shortest [2.8254(7)-2.8289(7) angstrom] and longest [2.9420(5) angstrom] intermolecular Au(I)center dot center dot center dot Au(I) contacts, respectively, and consequently they show the respective lowest (604 nm) and highest (554 nm) luminescence energies. Indeed, 2 center dot solvates exhibit different types of time-dependent luminescence upon solvate loss in air. Furthermore, B3LYP/LanL2DZ calculation results can help to clarify the relationship between intermolecular Au(I)center dot center dot center dot Au(I) contacts and luminescence energies for 2 center dot solvates.