The structures formed by sulfur adsorbed on the Rh(111) surface have been studied with Auger electron spectroscopy (AES), low-energy electron diffraction (LEED) and scanning tunneling microscopy (STM). Five differently ordered overlayer structures were observed to form as a function of coverage. These are: ([radic ]3 [times ] [radic ]3)R30[deg ], c([radic ]3 [times ] 7)rect, c(4 [times ] 2), (4 [times ] 4) and (7 [times ] 7). The first structure forms up to 0.33 monolayers, with S occupying fcc hollow sites. Above 0.33, hcp hollow sites are occupied as well. In the c(4 [times ] 2) structure, at 0.5 monolayer coverage, there is equal occupation of fcc and hcp hollow sites. The transition from the ([radic ]3 [times ] [radic ]3)R30 to c(4 [times ] 2) overlayer occurs by formation of dense domain boundaries containing both fcc and hcp sites. The S in the hcp sites is metastable and, upon heating, it moves to nearest fee sites to produce the (4 [times ] 4) structure.