A new application for glycerol that expands its possibilities beyond a green solvent and a precursor of value-added products has been demonstrated. Simple, easily available, and environmentally friendly dioxomolybdenum(VI) complexes are highly efficient catalysts for the chemoselective sulfoxide deoxygenation with this biomass-derived chemical feedstock. Both refined glycerol and crude glycerin can be used, thus expanding the potential application of this reaction. Subsequent transformation of glycerol during this reductive process has also been investigated.