We report a joint experimental and theoretical study on the structures of a series of gold clusters doped with a sulfur atom, Au(x)S(-) (x = 2-5). Well-resolved photoelectron spectra are obtained and compared with theoretical results calculated using several density functional methods to elucidate the structures and bonding of Au(x)S(-) (x = 2-5). Au2S(-) is found to have an asymmetric linear global minimum structure with C(∞v) symmetry, while the most stable structure of neutral Au2S is bent with C(2v) symmetry, reminiscent of H2S. Au3S(-) is found to have an asymmetric bent structure with an Au-S-Au-Au connectivity. Two isomers are observed experimentally to co-exist for Au4S(-): a symmetric bent 1D structure (C(2v)) and a 2D planar low-lying isomer (C(s)). The global minimum of Au5S(-) is found to be a highly stable planar triangular structure (C(2v)). Thus, a 1D-to-2D structural transition is observed in the Au(x)S(-) clusters as a function of x at x = 4. Molecular orbital analyses are carried out to obtain insight into the nature of the chemical bonding in the S-doped gold clusters. Strong covalent bonding between S and Au is found to be responsible for the 1D structures of Au(x)S(-) (x = 2-4), whereas delocalized Au-Au interactions favor the 2D planar structure for the larger Au5S(-) cluster.