Dimethylsulfoxide is reduced by molecular hydrogen under mild conditions to dimethylsulfide and water in the presence of rhodium(III) complexes as catalysts. The kinetics of the systems using RhCl 3 .3H 2 O and cis-RhCl 3 (Et 2 S) 3 have been investigated, and a mechanism involving reduction of coordinated dimethylsulfoxide in a rhodium(III) hydride complex is postulated. The catalytic efficiency of the systems decreases slowly due to the production of inactive rhodium(I) species.