An efficient short protocol for the preparation of N-perfluoroacylated glycals of neuraminic acid, by simple short treatment of differently protected N-acetylneuraminic acid with perfluorinated anhydrides in acetonitrile at 135 °C, is reported, together with a rationalitazion of the reaction that allows the alternative formation of N-perfluoroacylated 1,7-lactones to be previewed under the same reaction conditions.