A series of cationic rhodium(I) complexes [Rh(diene)(N^N)][BF 4] (diene = 1,5-cyclooctadiene (cod), norbornadiene (nbd), tetrafluorobenzobarralene (tfb)), containing the optically pure bis(sulfoximine) ligand 1,2-bis( S-methyl- S-phenylsulfonimidoyl)benzene, have been synthesized and fully characterized. The structure of the R, R enantiomer of the ligand, and that of its cyclooctadiene–Rh(I) complex, were confirmed by means of single-crystal X-ray diffraction techniques. Studies on the catalytic activity of these complexes in acetophenone hydrosilylation and dimethyl itaconate hydrogenation are also reported.