Full title. Luminescent phosphine gold(I) thiolates: Correlation between crystal structure and photoluminescent properties in [R₃PAu{SC(OMe)=NC ₆H₄NO₂-4}] (R = Et, Cy, Ph) and [(Ph ₂P-R-PPh₂){AuSC(OMe)=NC₆H₄NO ₂-4}₂] (R = CH₂, (CH₂)₂, (CH₂)₃ (CH₂)₄, Fc). X-ray crystallography shows the gold atoms in [R₃PAu{SC(OMe)= NC₆H₄NO₂-4}] (R = Et, Cy, Ph; 1-3, respectively) and [(Ph₂P-R-PPh₂){AuSC(OMe)=NC ₆H₄NO₂-4}₂] (R = CH₂, (CH₂)₂, (CH₂)₃, (CH ₂)₄, Fc; 4-8, respectively) are linearly coordinated by phosphorus and thiolate-sulfur; weak intramolecular Au⋯O interactions are featured in all structures. The smaller ethyl substituents in 1 allow for supramolecular association via Au⋯S and Au⋯Au interactions that are not found in 2 and 3, which contain larger phosphorus-bound Cy and Ph groups, respectively. Intramolecular Au⋯Au interactions are found in the dppm, dppe, dppp, and Fc structures but not in the dppp analogue, for which an anti conformation was found. The structures have been correlated with the results from photophysical study conducted in the solid state. Thus, photoexcitation of 1-7 with λ > 350 in the solid state and in solution produces green and blue luminescence, respectively. The spectra in each medium are remarkably similar to each other, and so the emission energy and excitation maxima observed for 1-7 appear to be independent of the nature of the ancillary phosphines, as well as the presence or absence of Au⋯Au interactions, either intermolecularly or intramolecularly.