A series of discrete compounds and supramolecular polymers were synthesized by self-assembly of dithioether building blocks and HAuCl4.3H2O. In complexes 1 {[AuL(1-Me)Cl], where L(1-Me) is bis(methylthio)methane} and 2 {[Au2L(2-Ph)Cl2], where L(2-Ph) is 1,2-bis(phenylthio)ethane}, adjacent units are connected via aurophilic interactions. Complex 1, a one-dimensional (1D) supramolecular polymer, and complex 2, a two-dimensional supramolecular network, both feature nearly linear [Au-Au-](infinity) chains. Complexes 4a, 4b, and 4c, all of which contain 1,3-bis(phenylthio)propane (L(3-Ph)), are polymorphs having the composition [Au2L(3-Ph)Cl2]. Complex 3 {[Au2L(1-Ph)Cl2], where L(1-Ph) is bis(phenylthio)methane}and complexes 4a and 4b consist of nearly identical 1D supramolecular polymers formed through Au-Au interactions. The third polymorph, 4c, is a molecular complex, as it does not have metal-metal interactions. Complex 5 {[Au2L(4-Ph)Cl2], where L(4-Ph) is 1,4-bis(phenylthio)butane} is also molecular. UV-vis spectra showed that the absorption bands of these complexes are allowed ligand-centered transitions between 230 and 260 nm. Complexes 1, 2, and 6 {[AuL(3-Me)Cl], where L(3-Me) is 1,3-bis(methylthio)propane} exhibited solid-state luminescence at 5 K with vibronic progressions and band maxima at approximately 570 nm. It is suggested that complex 6 contains [Au-Au-](infinity) chains.