Al(III) complexes derived from aminotriphenolate ligands are shown to be excellent catalysts for the formation of cyclic sulphites from a range of (functionalized) terminal and internal epoxides, and ex situ generated sulphur dioxide. The developed catalytic protocol is characterized by its operational simplicity, wide scope in epoxide reaction partners, good to excellent isolated yields and mild reaction conditions (5070oC, p(SO2) < 1 bar). The synthetic potential of these cyclic sulphites in organic synthesis is demonstrated in the preparation of N-substituted aziridines through a three-step protocol.