AbstractA general and straightforward procedure for the lithiation trapping of cyclic sulfides such as tetrahydrothiophene, tetrahydrothiopyran and a thiomorpholine is described. Trapping with a wide range of electrophiles is demonstrated, leading to more than 50 diverse α‐substituted saturated sulfur heterocycles. The methodology provides access to a range of α‐substituted cyclic sulfides that are not easily synthesised by the currently available methods.