Ionic gold(I) complexes with general formula of [Au(Py)(2)][AuCl2] and [Au(Py)(2)][PF6] (Py = 4-substituted pyridines) have been synthesized. Structures of five Au(I) complexes and a Ag(I) complex were determined by single crystal X-ray diffraction. Evidence for cationic aggregation of [Au(Py)(2)][PF6] complexes in solution was obtained by conductivity measurements and by the isosbestic point observed from variable temperature UV-visible absorption spectra. All compounds were luminous in the solid state. Calculations employing density functional theory were performed to shed light on the nature of the electronic transitions. While the [Au(4-dmapy)(2)][AuCl2] (4-dmapy = 4-dimethylaminopyridine) and [Au(4-pic)(2)][AuCl2] (4-pic = 4-picoline) emissions were found to be mainly ligand in nature, their [PF6](-) counterparts involved a Au center dot center dot center dot Au-interaction imbedded in the highest occupied molecular orbital. [Au(4-dmapy)(2)][AuCl2] was found to be an efficient catalyst for Suzuki cross-coupling of aryl bromide and phenylboronic acid.