The synthesis and spectroscopic characterization of the stereoisomers of bis(tert-butilsulfinyl)methane and 1,1-bis(tert-butilsulfinyl)octane is reported. The stereoisomeric mixture of bis(tert-butilsulfinyl)methane, meso and dl pair compounds and stereoisomeric mixture of 1,1-bis(tert-butilsulfinyl)octane, were separated by chromatography and characterized by NMR techniques. The corresponding oxidation products of bis(tert-butilthio)methane: monosulfoxide, monosulfoxide-monosulfone and disulfone compounds were also synthesized.