We report the synthesis of six-membered saturated and unsaturated 1,4-oxasulfone derivatives via rongalite-mediated intermolecular double sulfination of α-bromoacetophenone. This was followed by Bi(OTf)3-catalyzed intramolecular condensation of 1,3-diaroylsulfones under open-vessel conditions. Furthermore, the chemical structures of the key products were determined through single-crystal X-ray analyses.