Dehydrocondensation reactions of silicon hydrides catalyzed by the rhodium(III) complex [RhCl₃(Me₂SO)₃] in the absence of the second substrate were studied. It was found that the complex [RhCl₃(Me₂SO)₃] catalyzed the dehydrocondensation reaction with the formation of compounds containing siloxane bonds. Analysis of NMR spectra has shown that the reaction of [RhCl₃(Me₂SO)₃] with silicon hydride includes sequential desoxygenation of sulfoxide ligands to sulfide ligands with the complex [RhCl₃(Me₂S)₃] formation.