The degradation of SF6 and SF5 organyls by S-F and S-C bond-activation reactions at [{Rh(μ-H)(dippp)}2] under mild conditions is reported. Fluorido and thiolato species were identified as products or intermediates, and were characterized by X-ray diffraction analysis and multinuclear NMR spectroscopy. An unprecedented cyclic process for the conversion of the potent greenhouse gas SF6 into H2S was developed.