Re(O)Cl(3)(PPh(3))(2), 1, and Re(O)Cl(3)(OPPh(3))(Me(2)S), 2, catalyze the oxidation of thiols to disulfides with sulfoxides under mild conditions. Catalyst 1 exhibits an induction period which features PPh(3) oxidation to OPPh(3) prior to disulfide formation. This lag is absent when 2 is the catalyst precursor. Otherwise, 1 and 2 display comparable kinetics and concentration dependencies. The catalytic reactions are first-order in catalyst, inhibited by thiol, and first-order in sulfoxide at low sulfoxide concentrations. Thiol inhibits the oxygen-transfer reaction because it competes with sulfoxide for coordination on rhenium. Sulfoxides must bind to rhenium in order to be activated for oxo transfer. Ligand substitution reactions of 1 and 2 display kinetics that are consistent with a dissociative (D) mechanism: the substitution rate is zero-order in entering ligand and inhibited by departing ligand. The first-order rate constant for the formation of a 5-coordinate intermediate is 0.06 s(-)(1). As the sulfoxide concentration is increased, the reaction rate increases to reach a maximum and then begins to decline. The catalytic turnover rate at optimal conditions (maximum k(cat) for PhS(O)Me is 180 h(-)(1)) approaches the rate of ligand substitution in these rhenium(V) complexes. Rate retardation at high sulfoxide concentrations is due to catalyst deactivation; sulfoxides oxidize the rhenium(V) catalyst to ReO(4)(-), which is inactive. Dimethyl sulfoxide (DMSO) is more efficient than aryl sulfoxides at oxidizing the catalyst, a fact that could be rationalized by the thermodynamics of S-O bond strength. Thus, aryl sulfoxides, such as PhS(O)Me, appear to be more reactive than alkyl ones. The oxygen-transfer reaction, therefore, is not involved in the rate-controlling step and the rate is limited by ligand substitution. The rhenium(V) catalyst in these reactions acts as a Lewis acid and activates the sulfoxide via coordination: the sulfoxide ligand and not the metal is the bearer of the transferred oxygen. A single-crystal X-ray structure of Re(O)Cl(3)(OPPh(3))(Me(2)S), 2, has been solved: space group Pcmn, a = 8.863(6) Å, b = 14.269(9) Å, c = 18.45(1) Å, Z = 4; the structure was refined to final residuals R = 0.028 and R(w) = 0.035.