A methyl 2-trifluoromethyl-2-siloxycyclopropanecarboxylate was smoothly deprotonated by lithium diisopropylamide and reacted with carbon disulfide and methyl iodide to afford a dihydrothiophene derivative. The crucial step in this transformation is a ring-expansion of the anionic intermediate by [1,3] sigmatropic rearrangement. The dihydrothiophene was converted into the corresponding 5-trifluoromethylthiophene derivative by phosphoryl chloride in refluxing pyridine. A one-pot version of the reaction sequence efficiently provided the thiophene in good yield. Analogously, aryl- and alkyl-substituted isothiocyanates instead of carbon disulfide afforded the corresponding trifluoromethyl-substituted pyrroles in moderate to very good overall yields. Explorative reactivity studies with the methylthio-substituted thiophene and pyrrole derivatives demonstrate that they are precursors of a range of interesting trifluoromethyl-substituted products, including new members from the thienothiophene and thienopyrrole class.