The preparation and crystal structures of 3,3 ''-diethynyl-2,2':5',2 ''-terthiophene (A(2)T(3)) and three Au(I) complexes containing this ligand are reported. One of the complexes, Au-2(dppm)(A(2)T(3)), has a short Au-Au distance (3.1969 angstrom) because of an aurophilic interaction. UV/vis absorption and emission spectra of the complexes and ligand at 298 and 85 K and photoinduced electron transfer to methyl viologen are reported. A(2)T(3) and two of the complexes may be electropolymerized, and the resulting gold-containing films were characterized by X-ray photoelectron spectroscopy (XPS) and cyclic voltammetry.