ABSTRACT The base‐promoted in situ generation of pentafluoropropanenitrile from pentafluoropropanal O ‐(2,4‐dinitrophenyl) oxime derived from R115 has been developed. The pentafluoropropanenitrile obtained by this methodology was employed as a highly reactive electrophilic reagent in a cycloaddition reaction with a variety of dipoles to afford pentafluoroethylated heterocycles in moderate to excellent yields.