Molecular rearrangements of O-N bond-containing azoles (1-oxa-2- azoles) represent a wide class of reactions by which various heterocycle-toheterocycle transformations can be performed as alternative synthetic methodologies. The material presented in this review is an extensive survey of both thermal and photochemical methodologies that have been applied to fluorinated oxadiazoles, and shows how molecular rearrangements can be an alternative and in some cases the most convenient route for the synthesis of several fluorinated heterocycles.