The dirhodium(II) carboxylate complex Rh2(esp)2 (esp = α,α,α',α'-tetramethyl-1,3-benzenedipropanoate) was shown to catalyze the sulfoxidation of organic sulfides using tert-butyl hydroperoxide as the oxidant. Due to the unique structure of Rh2(esp)2 and its stable Rh2(II,II) catalyst resting state, the rhodium catalyst is able to precipitate as a Rh2(esp)2-sulfoxide complex following the reaction which makes separation of the catalyst from the products very convenient. The precipitated Rh2(esp)2-sulfoxide complexes could be reused to catalyze sulfide oxygenation reactions without considerable loss of activity. Mechanistic studies suggest that the axial ligands fine-tune the redox potential of the dirhodium(II,II) compounds and determine the predominant catalyst species in the oxidation reaction.