The crystal structures of R3PAu[SC6H4C(=O)NH2-2], R = Et (1), Ph (2), and Cy (3) show linear coordination geometries for gold defined by sulfur and phosphorus atoms. Supramolecular aggregation via {...H-N-C=O}2 synthons lead to dimeric aggregates in each case. In (1) and (2), the aggregates are spherical, but steric effects exerted by cyclohexyl rings in (3) dictate a rodlike form; no Au...Au interactions were noted in the crystal structures. Solvent dependence in their NMR spectra is correlated with intra- and intermolecular hydrogen bonding. The compounds uniformly decompose under controlled conditions to give gold. The complexes excited by UV light produce strong blue-green luminescence. The configuration interaction singles (CIS) post-Hartree-Fock (HF) calculations for the compounds indicate that it is the charge transfer from the sulfur and pi-orbitals of SC6H4C(=O)NH2-2 to gold that produce the emission from gold. The assignment of the observed luminescence is presented in terms of the relaxed excited states of gold, in which the vibronic interactions for three p-orbitals of gold are taken into account.