O-Phthalimide oximes with an NON fragment were synthesized in high yields via the reaction of vinyl azides with phthalimide-N-oxyl radicals derived from N-hydroxyphthalimide under the action of cerium(IV) ammonium nitrate. The disclosed process is based on the radical transformation of vinyl azides with the elimination of nitrogen and the formation of iminyl N-radicals. The developed approach exploited the dual reactivity of imide-N-oxyl radicals. They act as O-components for oxidative CO coupling with vinyl azides and participate in subsequent formation of the NO bond via their recombination with intermediate iminyl radicals.