With a view to synthesize 2-(trifluoromethylthio)-1,3-dithiane (1), 1,3-dithiane (2) was reacted in dry pentane at −78°C under dry N2 with trifluoromethylsulfenyl chloride (3) and was found to furnish the desired compound in poor yields along with ten other compounds. Under similar conditions, 2-lithio-1,3-dithiane on treatment with 2 and bis-(trifluoromethyl)disulfide (4) gave 8.0% and 10.0% yields of 1, respectively. In connection with this study, (cholromethyl) propyl sulfide and bis-(propylthio)methane were synthesized. The reaction of the latter with 3 was also investigated. The characterization of the primary compound formed in the reaction of 2 with 3 using the ‘INAPT ’-NMR and GC-MS, the probable mechanism of the formation of the various compounds and their mass spectral identification are presented in this article.