We developed a novel strategy for selective rearrangement of oxaziridines to nitrones via 1,1,1,3,3,3-hexafluoroisopropyl alcohol (HFIP)-mediated activation. Oxaziridines can generate nitrones by using HFIP that possesses some beneficial chemical properties as solvent. This developed reaction was conducted under mild conditions without any additives with excellent functional group tolerance and yields.