The selective assembly of the 1,4-oxathiin nucleus has been treated as a powerful strategy to access this scaffold present in molecules with very interesting properties. In this study, the chameleon-like reactivity of pyridinium 1,4-zwitterionic thiolates is exploited to assemble the 1,4-oxathiin core through a [3 + 3] annulation. The optimal annulation partner has been found to be the iodonium ylide of the cyclic 1,3-diketones. The developed protocol allows the synthesis of a variety of bicyclic 1,4-oxathiin derivatives under very mild conditions under copper(I) iodide catalysis. Access to benzoannulated 1,4-oxathiins has been achieved through iodine-mediated aromatization of the initially obtained bicyclic compounds.