N-Oxyl radicals (compounds with an N–O^• fragment) represent one of the richest families of stable and persistent organic radicals with applications ranging from catalysis of selective oxidation processes and mechanistic studies to production of polymers, energy storage, magnetic materials design and spectroscopic studies of biological objects. Compared to other N-oxyl radicals, oxime radicals (or iminoxyl radicals) have been underestimated for a long time as useful intermediates for organic synthesis, despite the fact that their precursors, oximes, are extremely widespread and easily available organic compounds. Furthermore, oxime radicals are structurally exceptional. In these radicals, the N–O^• fragment is connected to an organic moiety by a double bond, whereas all other classes of N-oxyl radicals contain an R₂N–O^• fragment with two single C–N bonds. Although oxime radicals have been known since 1964, their broad synthetic potential was not recognized until the last decade, when numerous selective reactions of oxidative cyclization, functionalization, and coupling mediated by iminoxyl radicals were discovered. This review is focused on the synthetic methods based on iminoxyl radicals developed in the last ten years and also contains some selected data on previous works regarding generation, structure, stability, and spectral properties of these N-oxyl radicals. The reactions of oxime radicals are classified into intermolecular (oxidation by oxime radicals, oxidative C–O coupling) and intramolecular. The majority of works are devoted to intramolecular reactions of oxime radicals. These reactions are classified into cyclizations involving C–H bond cleavage and cyclizations involving a double C=C bond cleavage.