The adsorption of tert-butyl thioalcohol on clean and sulfided Au(110) surfaces has been investigated with temperature programmed reaction spectroscopy. About half of the thiol adsorbed at 100 K undergoes S-H bond cleavage below 300 K to form tert-butyl thiolate; H-2 and H2S are evolved between 150 and 350 K, the relative amounts depending on the surface sulfur coverage. tert-Butyl thiolate decomposes above 400 K on both clean and sulfided Au(110) surfaces via several competing processes to yield tert-butyl thioalcohol, isobutene, and H2S in the gas phase, together with adsorbed sulfur. The mechanism by which this reaction occurs is dominated by gamma-H transfer to either coadsorbed tert-butyl thiolate or sulfur-organometallic reactions which may be unique to surfaces.