Benzenethiol reactions on clean and hydrogen precovered Ni(100) surfaces have been studied in order to characterize C-S bond breaking. Benzenethiol adsorbs at 90 K as phenylthiolate and surface hydrogen. The dominant benzene formation pathway for large coverages of benzenethiol occurs at 270 K. C-S bond breaking involves direct reaction of phenylthiolate with the nickel surface; hydrogen does not appear to be directly involved. The rate-limiting C-S bond breaking step is followed by rapid hydrogenation of adsorbed phenyl to form benzene which desorbs from the sulfur covered surface. Deuterium incorporation studies support this mechanism since single hydrogen addition dominates as expected for hydrogenation of an adsorbed phenyl intermediate. For the benzenethiol saturated surface (0.30 monolayer), hydrogen preadsorption increases the temperature for benzene formation by up to 20 K and increases the benzene yield up to 37%. Reorientation of the phenylthiolate away from the surface in the presence of large coadsorbed hydrogen coverages is indicated by vibrational characterization. This hydrogen induced reorientation appears to be associated with the increase in C-S bond activation energy. Above 500 K dehydrogenation of adsorbed phenylthiolate derived species results in formation of surface bound polyaromatic hydrocarbons (PAHs) coadsorbed with sulfur; the hydrogen formed in this process desorbs. For low coverages of benzenethiol, no 270 K benzene is observed due to increased dehydrogenation by the surface. A small amount of benzene is formed by disproportionation above the temperature of free hydrogen desorption (400 K). A comparison of benzenethiol reactions on the three low Miller index surfaces of nickel clearly indicates that hydrogen availability at reaction temperature has a large influence on benzene formation. Hydrogen desorption prior to C-S bond activation on the Ni(100) surface limits benzene formation, while substantial hydrogen availability on the Ni(111) and Ni(110) surfaces facilitates benzene formation.