A similar effect to the well-known reverse Perlin effect was observed on the 1JC–F coupling constants of α- and β-d-glucopyranosyl fluoride tetracetate, both in nonpolar and polar solution. This can be called “reverse fluorine Perlin-like effect”, and it is shown to be ruled by dipolar interactions rather than by hyperconjugation. The reverse fluorine Perlin-like effect does not have a general relationship with the anomeric effect, and it can be useful to determine the structure and stereochemistry of organofluorine compounds.